Graphene Roadmap

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FOCUS | FEATURE

Things you could do with graphene


Graphene and its derivatives are very versatile materials. As a result of their electrical, mechanical and optical
properties they have, in the past 10 years, been proposed for use in a wide range of applications ranging from
flexible electronics to DNA sequencing. They offer the promise to significantly improve existing products
and to enable the design of materials and devices with novel functionalities. We asked seven experts in their
fields to share their views on the potential and challenges in the realization of graphene-based products in a
range of technologies. Development of graphene materials and devices is more mature in some areas, such as
flexible electronics and conductive inks, but is at a more conceptual stage in others, such as biomedical and
aerospace technologies. Several challenges towards commercialization remain that are application-dependent.
Furthermore, a common problem for the introduction of graphene in industrial applications is the lack of
methods for the large-scale production of graphene materials, in particular of electronic-quality layers.

Graphene for displays that bend


Jong-Hyun Ahn and Byung Hee Hong discuss how graphene can be used in the development of
flexible electronics.
transparent conductors characterized so
far3. Synthesis by CVD is also advantageous
because it consumes only tiny amounts of
carbon gases and does not need rare mineral
resources such as indium or silver. The
catalytic metal substrate is also reusable, and
recycling technology is industrially available.
The use of graphene as a transparent
electrode has already been demonstrated
in a variety of flexible optoelectronic
devices, including touch-screen sensors4
(Fig.1), organic light-emitting diodes5
and organic photovoltaic devices6. The

possibility of fabricating lightweight, thin


and low-cost flexible electronics devices
through continuous roll-to-roll processes
is another important advantage of using
graphene electrodes4.
Despite this, considerable challenges must
be overcome to integrate graphene-based
transparent electrodes into commercial
devices. These include the development of
a low-cost, large-scale synthesis method
for high-quality graphene with guaranteed
uniformity and reproducibility 7; a defectand residue-free transfer method that

GRAPHENE SQUARE INC.

lectronic components that are flexible


and stretchable are more versatile than
rigid ones, and are sought after for
optoelectronic devices such as displays, solar
cells and light emitters. Flexible components
need to be fabricated on soft substrates
such as plastic or rubber, but traditional
fabrication methods use a rigid substrate,
and therefore new materials and processes
are required. In optoelectronic devices,
transparent electrodes are key components,
and at present are typically made from
indium tin oxide (ITO) because of its
relatively good conductivity and optical
transparency. But ITO has poor mechanical
properties: when bent or stretched it tends
to crack, and this leads to a deterioration of
its electrical properties.
Graphene has emerged as a promising
material for transparent and flexible
electrodes. The optical transmittance of
monolayer or few-layer graphene grown
by chemical vapour deposition (CVD)1 is
superior to that of ITO and other emerging
materials, and the sheet resistance of
graphene films is comparable to that of
ITO because of graphenes high carrier
mobility (>103 cm2V1s1) and high carrier
density (>1012cm2 for doped samples)2.
Furthermore, graphene on flexible substrates
is mechanically robust, and has the
smallest bending radius among all exible

Figure 1 | Graphene-based multi-touch screen showing excellent flexibility (left)7 and possible
applications in bendable or foldable mobile devices (right).

NATURE NANOTECHNOLOGY | VOL 9 | OCTOBER 2014 | www.nature.com/naturenanotechnology

2014 Macmillan Publishers Limited. All rights reserved

737

FEATURE | FOCUS
is compatible with conventional device
manufacturing processes8; doping processes
that can assure stable, high electrical
conductivity over long periods9; a method
to improve the environmental stability of
graphene electrodes against moisture and
chemicals in the air 10; and a method to
decrease the contact resistance between
electrodes and active materials11.
One issue, in particular, with CVDgrown graphene is that it must be
transferred to a perfectly flat surface.
Most electronic devices, however, have an
interconnected, multilayered structure.
Although this is not a problem for ITO, as
it can be sputtered onto irregularly shaped
surfaces, the device architecture needs to
be customized for two dimensions when
using graphene electrodes. This limits
the immediate replacement of ITO by
graphene. Because of this, we anticipate that
applications to flat and simple structures

such as touch screens, smart windows,


electromagnetic interference shields, lighting
and transparent heaters12 will be the first to
be realized, whereas applications to flexible
displays and microelectronic devices will
follow some years later.
We expect that the market for flexible
electronics will become larger than that for
non-flexible electronics in about 10years.
Although there are many candidates for ITO
replacement including metal meshes and
silver nanowires whose sheet resistances are
as low as ~10sq1 at ~90% transmittance2
none of them are as flexible as graphene.
For example, the conducting properties of
graphene can remain stable up to ~11%
extension1, and its initial sheet resistance
persists for ~300,000 cycles at 3% bending
strain7, whereas a silver nanowire breaks
easily at strains of less than 1%13.
Resolving the above-mentioned
challenges will bring closer the advent of

flexible electronics, in which graphene


technology will be as stretchable as
ourimagination.

Jong-Hyun Ahn is at the School of Electrical and


Electronic Engineering, Yonsei University, Seoul,
Korea. Byung Hee Hong is in the Department of
Chemistry, Seoul National University, Seoul, Korea.
e-mail: [email protected]; [email protected]
References

1. Kim, K.S. et al. Nature 457, 706710 (2009).


2. Bonaccorso, F., Sun, Z., Hasan, T. & Ferrari, A.C. Nature Photon.
4, 611622 (2010).
3. Bae, S.H. et al. ACS Nano 7, 31303138 (2013).
4. Bae, S. et al. Nature Nanotech. 5, 574578 (2010).
5. Han, T.-H. et al. Nature Photon. 6, 105110 (2012).
6. Kim, K. et al. ACS Appl. Mater. Interfaces 6, 32993304 (2014).
7. Ryu, J. et al. ACS Nano 8, 950956 (2014).
8. Kang, J. et al. Nanoscale 4, 55275537 (2012).
9. Kim, S.J. et al. Chem. Mater. 26, 23322336 (2014).
10. Yan, C. et al. ACS Nano 6, 20962103 (2012).
11. Park, J. et al. J.Phys. Chem. Lett. 2, 841845 (2011).
12. Kang, J. et al. Nano Lett. 11, 51545158 (2011).
13. Leach, A.M., McDowell, M. & Gall, K. Adv. Funct. Mater.
17,4353 (2007).

Electrifying inks with 2D materials


Felice Torrisi and Jonathan N. Coleman describe how graphene can be used in conductive inks to print
electronic circuits.

tags, light-emitting diodes, batteries and


transistors, can be built by printing liquiddispersed functional materials such as organic
polymers, nanoparticles and nanotubes.
Techniques including inkjet, roll-to-roll and

STUART BRADFIELD

rinted electronics1,2 has recently emerged


as an important new direction for
electronics beyond conventional siliconbased technologies. Electronic devices,
including radiofrequency identification

738

spray deposition can pattern these materials


on either rigid or flexible substrates, at low
temperature and over large areas, and most
importantly at very low cost. However, the
performance of printed devices is limited
by the quality of the materials contained in
the inks and how these are arranged on the
target substrate. Graphene and other twodimensional (2D) materials are solutionprocessable and have useful physical and
chemical properties. Can they make an
impact on printed electronics?
Electronic inks are mixtures of a
functional material, stabilizers and rheology
modifiers. Different inks are needed to
print the different elements of devices:
semiconducting inks (the functional
materials) in the active layer, insulating
materials for dielectrics, and conducting
materials for electrodes. They must be
stable, cheap and print easily on appropriate
substrates to produce devices with high
charge-carrier mobility and long lifetime,
without the need for aggressive posttreatments. Finding materials that fulfil
these requirements is difficult. For example,
conducting inks often contain metallic
nanoparticles that may require sintering at
high temperatures to maximize conductivity,
which is problematic for polymeric

NATURE NANOTECHNOLOGY | VOL 9 | OCTOBER 2014 | www.nature.com/naturenanotechnology

2014 Macmillan Publishers Limited. All rights reserved

FOCUS | FEATURE
substrates. Furthermore, polymer-based inks
often lack stability whereas nanotube inks
are generally unsuitable for semiconducting
applications owing to the presence of both
metallic and semiconducting nanotubes.
Graphene has the potential to fulfil most
requirements for use in conducting inks
thanks to its high carrier mobility, mechanical
robustness, environmental stability and
potential for low-cost production. Before an
ink can be produced, graphene must first be
dispersed as nanosheets in a liquid. Graphene
suspensions can be produced from graphite
by oxidation to produce graphene oxide,
or by liquid-phase exfoliation in solvents
to give few-layer nanosheets3. Without
high-temperature or aggressive chemical
processing, however, it can be hard to achieve
high conductivities in films produced from
graphene oxide nanosheets. On the other
hand, large quantities of pristine nanosheets,
typically hundreds of nanometres across
and ~1nm thick, can be produced quickly
and easily by liquid-phase exfoliation in
readily printable liquids such as water and
organic solvents4. The resulting ink is stable,
processable in ambient conditions, and has
high batch-to-batch reproducibility as well
as good rheological properties for printing
and coating 5. Continuous networks of
graphene nanosheets have been produced
by methods such as spraying, filtration and
rod coating, and tend to have conductivities
of up to 104 Sm1 (ref. 6), even without
high-temperature or chemical treatments79.
They have performed well in applications
such as electrodes for supercapacitors, as
well as transparent electrodes for liquidcrystal displays, thin-film transistors and
smart windows5,8,9. Patterned networks, with
features as small as 30 m (ref. 10), have
been produced by inkjet printing 5,7 and
gravure coating 10, and have shown promise
in applications from supercapacitors11
to antennae12.
Although graphene can be used in
flexible interconnects or as an active
material in printed supercapacitors or

composite devices5,9, its lack of a bandgap


means that it cannot replace conjugated
polymers2 as the semiconducting material
in printed electronic devices. In addition to
graphene, however, liquid-phase exfoliation
can produce suspensions of a range of other
2D nanosheets, including WS2, MoO3 and
BN (ref. 3). These 2D materials have diverse
properties, with some being semiconductors
or insulators and some electrochemically
active, making their inks suitable for a wide
range of applications as active materials in
printed electronics. Spray coating 13 or inkjet
printing 14,15 of MoS2 nanosheets have been
recently reported for supercapacitor and
sensing applications.
But the most exciting applications of
2D materials in printed electronics will
come from printing devices where two or
more nanomaterials are integrated together
in well-defined structures. All-inkjetprinted heterostructure photodetectors and
transistors have already been produced by
sequential printing of graphene and WS2,
MoS2 or BN (refs 7,16). It is likely that
many developments will stem from these
pioneering works.
Nevertheless, a number of important
hurdles remain before these developments
can lead to commercialization of 2D materialbased inks. For example, although nanosheets
can be made in large quantities by liquidphase exfoliation, the yield of monolayers is
is still low, typically on the order of 525%,
and the flake size is poorly controlled. For
inkjet printing, the nanosheet size and the
rheological properties of the suspension
must be carefully tuned5. Furthermore, the
high aspect ratio of nanosheets generally
results in low-concentration suspensions
(~0.011wt%), which is problematic
for some printing techniques. Electrical
performance is another issue. Printed devices
will consist of networks of either graphene or
inorganic nanosheets, and charge transport
will be limited by junctions between the
sheets, resulting in mobilities typically two
orders of magnitude lower than in individual

nanosheets17. This will limit the achievable


conductivity of graphene interconnects,
and reduce the performance of devices
based on semiconducting nanosheets.
On the other hand, as MoS2 nanosheets
have mobilities of hundreds of cm2V1s1,
production of MoS2 networks with mobilities
of a few cm2V1s1 might be possible,
making them competitive with printed
conjugated-polymer-baseddevices2.
We believe that the future is bright for
printed devices based on 2D materials,
although many challenges remain. As new
materials combinations are demonstrated, the
range of printed devices and applications will
expand. Moreover, as the scaling up of ink
production proceeds, costs will fall, eventually
allowing the best 2D material-printed devices
to compete with traditional technologies on
cost and possibly performance.

Felice Torrisi is at the Cambridge Graphene Centre,


Engineering Department, University of Cambridge,
9 JJ Thomson Avenue, Cambridge CB3 0FA,UK.
Jonathan N.Coleman is at the CRANN and
AMBER Research Centres and the School of Physics,
Trinity College Dublin, Dublin 2, Ireland.
e-mail: [email protected]
References

1. Kamyshny, A. & Magdassi, S. Small 10, 35153535 (2014).


2. Baeg, K-J., Caironi, M. & Noh, Y-Y. Adv. Mater.
25, 42104244 (2013).
3. Nicolosi, V., Chhowalla, M., Kanatzidis, M.G., Strano, M.S. &
Coleman, J.N. Science 340, 1226419 (2013).
4. Paton, K.R. et al. Nature Mater. 13, 624630 (2014).
5. Torrisi, F. et al. ACS Nano 6, 29923006 (2012).
6. De, S. & Coleman, J.N. ACS Nano 4, 27132720 (2010).
7. Finn, D.J. et al. J.Mater. Chem. C 2, 925932 (2014).
8. Mendoza-Sanchez, B., Rasche, B., Nicolosi, V. & Grant, P.S.
Carbon 52, 337346 (2013).
9. Bonaccorso, F. et al. Mater. Today 15, 564589 (December, 2012).
10. Secor, E.B. et al. Adv. Mater. 26, 45334538 (2014).
11. Li, J. et al. Adv. Mater. 25, 39853992 (2013).
12. Shin, K.Y., Hong, J.Y. & Jang, J. Adv. Mater. 23, 21132118 (2011).
13. Cao, L. et al. Small 9, 29052910 (2013).
14. Li, J., Naiini, M.M., Vaziri, S., Lemme, M.C. & stlin, M.
Adv.Funct. Mater. http://dx.doi.org/10.1002/adfm.201400984
(2014).
15. Yao, Y.G. et al. Adv. Funct. Mater. 23, 35773583 (2013).
16. Withers, F. et al. Nano Lett. 14, 39873992 (2014).
17. Eda, G., Fanchini, G. & Chhowalla, M. Nature Nanotech.
3,270274 (2008).

Charging graphene for energy


Energy storage is a grand challenge for future energy infrastructure, transportation and consumer electronics. Jun Liu
discusses how graphene may or may not be used to improve various electrochemical energy storage devices.

raphene has captured the imagination


of researchers for energy storage
because of its extremely high
theoretical surface area (2,630 m2g1)

compared with traditional activated carbon


(typically below 1,500m2g1), excellent
electrical conductivity, high mechanical
strength and potential for low-cost

NATURE NANOTECHNOLOGY | VOL 9 | OCTOBER 2014 | www.nature.com/naturenanotechnology

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manufacturing. These properties are very


desirable for achieving high capacity and
energy density, and fast charge and discharge
rates. Graphene sheets used in energy
739

FEATURE | FOCUS
storage research are usually prepared by
oxidation and reduction of graphite1. Even
though these chemically derived graphene
materials contain multiple stacked graphene
sheets, structural defects (such as vacancies)
and oxidized functional groups, they are
more suitable for energy storage applications
than single-layer graphene, because they
can be made in relatively large quantities.
In the literature they are also called reduced
graphene oxide, or functionalized graphene
sheets, but here they are all referred to as
graphene for ease of discussion.
Two important devices batteries and
electrochemical capacitors have been
widely investigated. In a battery material, the
redox reaction occurs at a stable voltage, and
the energy is stored in the bulk. Therefore,
the energy density is high (more than
100Whkg1), but it is difficult to charge
or discharge the device rapidly (power
density is less than 1kWkg1; ref.2). In
an electrochemical capacitor (also called
supercapacitors or ultracapacitors in the
literature), the energy is stored as adsorbed
ionic species at the interface between the
carbon surface and the electrolyte. Thus,
charge and discharge can be rapid (power
density up to 10kWkg1) but the energy
density is low (less than 10Whkg1). A
device that could posses both high energy
and high power would be ideal.

Graphene is a great fit for electrochemical


capacitors. The fact that ion adsorption
occurs at the surfaces, and on the edges,
of the sheets means that the potential
at which the process takes place varies
continuously as a function of the surface
charge coverage, a primary requirement
for supercapacitive materials. Furthermore,
the unique combination of high surface
area and excellent electrical conductivity
makes graphene even more attractive3. The
theoretical specific capacitance of graphene
can be as high as 550Fg1 when all the
surface is used. As a comparison, typical
commercial electrochemical capacitors using
activated carbon have a capacitance of about
100Fg1. At present, the theoretical capacity
has not been achieved because graphene
sheets tend to restack in the electrode,
but values in the range 200300Fg1 have
been reported4.
Alongside electrochemical capacitors,
graphene has garnered enormous interest
as cathode and anode material for Li-ion
batteries5. Graphene sheets can have a
specific capacity greater than 500mAhg1,
which compares favourably with graphite
(372mAhg1), the anode material used in
commercial Li-ion batteries (Fig.1). For
a battery to work, however, the cathode
and the anode need to be charged and
discharged at different potentials, and the

Figure 1 | A schematic representation of a hybrid batterycapacitor device, in which an intercalation


material would be used as the cathode (left) and graphene as the anode material (right). Lithium ions
(yellow) are inserted and de-inserted during charge and discharge cycles. Figure reproduced with
permission from ref.16, 2011 Wiley.
740

operating voltage window is determined


by the difference between the discharge
potential of the cathode and the anode.
To achieve high capacity, graphene would
need to be charged at more than 3V.
Unfortunately, this does not seem realistic,
as anode materials should be charged
and discharged at less than 1V. At this
potential, graphene actually has a lower
specific capacity than commercial graphite.
Functionalized graphene sheets have also
been studied as cathode material6, but they
mostly exist in a delithiated state. As a result,
a Li-rich anode material, such as Li metal,
needs to be used. But the use of a Li-metal
anode introduces entirely new challenges,
as discussed later. Very recently, an allgraphene battery was explored7, partially
reduced graphene sheets are used as the
cathode, which can be charged to a high
voltage, and graphene oxide is used as the
anode. The battery shows both high energy
density (225Whkg1) and high power
density (6,450Wkg1), but how to make a
practical device remains unclear.
There are other promising ways to exploit
the properties of graphene for battery
applications. One of them consists in using
graphene as a coating material to enable the
direct use of Li-metal anodes. Lithium metal
has the highest capacity among all the anode
materials (3,860mAhg1), but it cannot be
used as is because it forms dendrites that
can potentially cause internal shortage and
thermal run-away (fire). In a new electrode
design, Li metal was coated with graphene
sheets that essentially function as highsurface-area capacitor materials, reducing
the current sustained by the Li metal itself,
and therefore reducing dendrite growth8.
Additionally, graphene could be exploited
to make composite materials with enhanced
electrical conductivity and mechanical
properties. It is well documented, for
example, that adding graphene to lowconductivity materials such as TiO2, LiFePO4
and organic materials can aid charge transfer
and promote high-rate chargedischarge
cycles. Moreover, ordered graphene
SnO2 sandwich structures or crumpled
grapheneSi composites possess enhanced
mechanical stability that can accommodate
the large volume change experienced by the
electrode during lithiation and delithiation
for improved cycling stability 9,10. The porous
structure of graphene-based materials, with
controlled functionalization density, has also
been explored for sulphur encapsulation for
LiS batteries11,12, devices with substantially
higher theoretical energy density
(2,600Whkg1) than Li-ion batteries13.
These designs provide new prospects for
energy storage, but the research is still in the
early stages.

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FOCUS | FEATURE
An under-explored territory is to use
graphene as a platform to understand
complex electrochemical reactions, as
the surface activity of graphene can be
controlled relatively easily by chemical
functionalization. This direction could
be especially useful to understand Liair
batteries. These devices have the highest
theoretical energy density (12,000Whkg1)
among known battery systems, but the
reactions occurring at the carbon cathode
to form the product, Li2O2, are poorly
understood and mostly irreversible14. In
some initial studies, functionalized graphene
sheets have been used to identify the active
sites on carbon mostly defects where
the desired Li2O2 phase forms15.
For practical applications, low-cost and
large-scale production methods need to be
developed. At present, industrial facilities
can produce around 100 tonnes of graphene
per year, but the quality and reliability of
this material (uniformity, particle sizes,
purity, surface area and carbon to oxygen
ratio) remain an issue. Moreover, graphene
production is still 5 to 10 times as expensive
as activated carbon or graphite, commonly
used materials in commercial electrochemical
capacitors and batteries. For capacitor and
battery applications graphene also needs
to be made in proper engineered forms.
Normally, graphene has very low packing
density (as low as 0.015gcm3), which
translates into very low volumetric energy
density in a device. In comparison, typical
graphite anode materials have a packing
density of about 1gcm3. Graphene sheets
also have a tendency to restack, reducing the
effective surface area, and may form twodimensional structures (such as layers parallel

to the electrode surface) that hinder ion and


electron transport across the electrode. As
a result, it is challenging to make practical
electrode materials with sufficient thickness
(more than 20m) to obtain meaningful
capacitance or capacity per unit area.
Either the materials supplier or the device
manufacturer needs to find ways to pack
graphene sheets into high-density aggregates
without sacrificing the surface area.
It is clear that graphene has great
potential, but it is not the panacea for
all problems in energy storage. The first
real application is likely to come from
electrochemical capacitors, assuming that
low-cost and high-quality graphene will
become available in large quantities and can
be made into the desired aggregate structure.
Graphene capacitors will be attractive for
grid applications that require fast response
time (milliseconds), high efficiency (over
95%), high power, long cycling life (more
than thousands of cycles), and variation
in the frequency caused by the power
mismatch of supply and demand. Graphene
capacitors will also find applications in
capacitorbattery hybrid devices for hybrid
and all-electrical vehicles to provide the
power for start-up and acceleration.
But claims in popular news that graphene
capacitors will make batteries obsolete are
premature. The truth is that batteries and
capacitors still fulfil quite different functions.
In the near future, it is also unlikely that
graphene will directly replace some of the
widely used anode or cathode materials in
Li-ion batteries just because it has a higher
specific capacity. To develop practical
electrode materials and devices, one must
consider the interplay of the intrinsic

properties of graphene, the overall structure


of the electrode, and the desired properties
and functions of the application, as well as
how the device will work. In the literature,
there is too much focus on achieving
high specific capacitance or high specific
capacity of graphene without considering
whether the whole chargedischarge
curve is appropriate for a real device and
even whether the positive and negative
electrodes will work together. Finally, there
is very limited research on how to make
the electrode material with a morphology
that can deliver good packing density,
and how the electrode material should be
incorporated into a real, stable device. It is
likely, however, that, in the medium term,
graphene will be used as an additive or
coating material for electrodes in Li-ion and
other battery applications to improve the
stability, capacity at fast discharge rate and
other electrochemical properties.

Jun Liu is at the Pacific Northwest National


Laboratory, Richland, Washington 99352, USA.
e-mail: [email protected]
References

1. Eda, G. & Chhowalla, M. Adv. Mater. 22, 23922415 (2010).


2. Conway, B.E. J.Electrochem. Soc. 138, 15391548 (1991).
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4. Yang, X. et al. Science 341, 534537 (2013).
5. Fan, Z. et al. Carbon 60, 558561 (2013).
6. Lee, S.W. et al. Nature Nanotech. 5, 531537 (2010).
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8. Zhamu, A. et al. Energy Environ. Sci. 5, 57015707 (2012).
9. Wang, D. et al. ACS Nano 4, 15871595 (2010).
10. Luo, J. et al. J.Phys. Chem. Lett. 3, 18241829 (2012).
11. Cao, Y. et al. Phys. Chem. Chem. Phys. Lett. 13, 76607665 (2011).
12. Yang, Y., Zhen, G. & Cui, Y. Chem. Soc. Rev. 42, 30183032 (2013).
13. Wang, H. et al. Nano Lett. 11, 26442647 (2011).
14. Shao, Y. et al. Adv. Funct. Mater. 23, 9871004 (2013).
15. Xiao, J. et al. Nano. Lett. 11, 50715078 (2011).
16. Cao, Y. et al. Adv. Mater. 23, 31553160 (2011).

Graphene against corrosion


Siva Bhm discusses how graphene can be used to prevent corrosion of metals such as steel.

orrosion is one of the greatest


challenges faced by the steel industry. It
is triggered by environmental factors,
such as water, oxygen and electrolytes. The
annual direct cost of metallic corrosion for
infrastructure (highway bridges, pipelines,
material storage), utilities (drinking water,
gas/electric), automotive transportation
and government defence is estimated to
be US$300 billion in the United States and
200 billion in Europe. Therefore, robust
and long-lasting solutions are required to
overcome corrosion issues. Until recently,

corrosion protection for steel was provided


by zinc- and chromium-based coatings;
however, because of the adverse effects
of chromium on human health and the
environment, its supply and use in Europe
are restricted. There is an increasing need for
more effective, environmentally friendly and
less costly products. Furthermore, innovative
technologies are shifting the focus from
protection against corrosion to its prevention.
Graphene has attracted attention for
applications in many industries since its
isolation in 20041. A graphene layer is made

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of carbon atoms arranged in a hexagonal


lattice, with each atom bonded to three
nearest neighbours within the plane by
sp2 hybridized orbitals. This results in a
high inherent strength of 0.142Nm along
carbon bonds, which makes graphene (in
the absence of defects) the strongest material
ever discovered, with an ultimate tensile
strength of 130GPa. Graphene has other
attractive properties, including electron
mobility up to 2.5105 cm2V1s1, thermal
conductivity of more than 3,000WmK1,
Youngs modulus of 1TPa and the capability
741

UNKAS_PHOTO/ISTOCK/THINKSTOCK

FEATURE | FOCUS

of sustaining high current densities2. In


particular, impermeability to all gases and
salts makes graphene an excellent candidate
in anticorrosion coatings.
In the past, fullerenes and exfoliated or
intercalated clay materials have been used
for anticorrosion applications, but those
materials are highly insulating and also
hydroscopic. Hydroscopic material acts
to suppress the anticorrosion behaviour
of the coating by increasing water uptake,
weakening the coatings barrier properties.
For coated metal substrates to be used in
some applications such as fuel cells and solar
cells, the coating needs to be electrically
conductive, as a fully insulating coating
isunsuitable.
Graphenes excellent electrical
conductivity and high surface area play
an important role in its anticorrosion
mechanism. As we currently understand it,
the anticorrosion mechanism provided by
graphene can be explained by a combination
of three processes. On the one hand,
graphene coatings can make the path of
permeating water more tortuous. Second,
because of the impermeability of pristine
graphene, the coatings act as an excellent
barrier to water, oxygen and other corrosive
materials. Furthermore, graphene has a
higher electrical conductivity than steel.
With polymeric anticorrosion coatings,
when the corrosion starts at the metal/
coating interface, electrons generated by
the anodic reaction move through the
metal to a cathodic site, and complete the
corrosion reaction. This is the reason that,
once the corrosion starts at the interface
of the metal and a conventional insulating
coating, it is difficult to stop. However, when
functionalized graphene is incorporated in
742

the coating, because of its excellent electrical


conductivity, an alternative path for the
electrons is provided, so that they may never
reach a cathodic site. Moroever, graphene
and graphene hybrid nanocomposites can
be used as inhibitors in protective coatings
to prevent oxidation of underlying metals
in oxidizing chemicals, water or air for
longerperiods37.
Recently, a highly versatile top-down
approach was proposed for industrial
production of graphene from graphite by
liquid exfoliation, which functionalizes
graphene and seamlessly incorporates it
into organic coatings3,4,8,9. Graphene-based
coatings showed an excellent corrosion
inhibition capability when compared
with current chromate-free anticorrosion
technology, and comparable performance to
chromate-based anticorrosion technology 6,7.
These graphene-based coatings have been
used for bipolar plates in fuel cells, which
are stainless steel components that separate
individual cells in a stack and aid in the
distribution of fuel and oxidant, water
management and current collection. The
high cost of bipolar plates is a limiting factor
for the mass-market commercialization
of fuel-cell stacks, and ways are sought to
reduce their costs or increase their durability,
for example by reducing corrosion of the
stainless steel in the fuel-cell environment.
Our electrochemical testing indicates that
two types of stainless steel with low carbon
content, SS304L and SS316L, corrode
severely in fuel-cell acid environments, at
rates of ~0.7and 0.5mmyr-1, respectively.
When considering the limited thicknesses
that can be used for bipolar plates, these
corrosion rates are very high. The use of
graphene-based coatings resulted in a

significant improvement of the performance


of coated stainless steel in the corrosive
environment compared with uncoated
stainless steel. With a submicrometre
graphene-based coating, the corrosion rates
of these materials were greatly decreased,
to under 0.000196mmyr1 for SS304L
and under 0.000859mmyr1 for SS316L
(unpublished results).
But the major concerns of the steel
industry over using graphene as a corrosion
inhibitor are its high production costs and
limited availability. Liquid-phase exfoliation
is a cost-effective, environmentally
friendly way of producing graphene,
in which naturally available graphite is
exfoliated by wet-chemical and mechanical
processing. The graphene produced by
this method, however, has far more defects
than chemically synthesized graphene
from carbon precursors. Even though the
latter suffers from high production cost,
it is easier to control the properties of the
graphene thus produced, by controlling the
process parameters.
In an anticorrosion application,
graphene has to be used as one component
in a multicomponent coating dispersion.
Incorporating graphene into such a
coating formulation is still a challenge.
Functionalizing graphene can be a solution.
The benefit is that the functionalization step
can be incorporated during the exfoliation
stage, making the whole formulation process
a single continuous one.
We foresee that graphene technology
will be incorporated into existing processes
to enhance products in markets already
served by the steel industry. Obviously, new
processes will need to be developed for the
new graphene-based products, but this is not
something the industry will shy away from.
Siva Bhm is at Tata Steel Research & Development
(Europe & India), Swinden Technology Centre,
Moorgate Road, Rotherham, South Yorkshire
S603AR, UK, and at IIT-Bombay, Department
of Metallurgy & Materials (ME&MS),
Powai-Mumbai 400 076, India.
e-mail: [email protected]
References

1. Novoselov, K.S. et al. Science 306, 666669 (2004).


2. Benerjee, K. et al. Appl. Phys. Lett. 97, 263109 (2010).
3. Bohm, S. et al. Environmentally friendly protective coatings for
metal substrate. Patent no. WO/2011069663 (2011).
4. Bohm, S., English, T. H., Hammond, D. & Melgari, P. Flexible dye
sensitized solar cell and a method for manufacturing the same.
Patent no. WO2013/100930 (2012).
5. Dennis, R.V., Viyannalage, L.T., Gaikwad, A.V., Rout, T.K. &
Banerjee, S. Am. Ceram. Soc. Bull. 92, 1824 (2013).
6. Kirkland, N.T., Schiller, T., Medhekar, N. & Birbilis, N.
CorrosionSci. 56, 14 (2011).
7. Chen, S. et al. ACS Nano 5, 13211327 (2012).
8. Prasai, D., Tuberquia, J.C., Harl, R.R., Jennings, G.K. &
Bolotin,K.I. ACS Nano 6, 11021108 (2012).
9. Tong, Y., Bohm, S. & Song, M. Austin J.Nanomed. Nanotechnol.
1,16 (2014).

NATURE NANOTECHNOLOGY | VOL 9 | OCTOBER 2014 | www.nature.com/naturenanotechnology

2014 Macmillan Publishers Limited. All rights reserved

FOCUS | FEATURE

Sequencing with graphene pores


Solid-state nanopores are often used for biomolecular analysis, but have so far been unable to sequence DNA.
Marija Drndi asks whether nanopores made in graphene could fulfil all of the requirements needed for sequencing.

IMAGE COURTESY OF ROBERT JOHNSON

olid-state nanopores can be used


to detect, analyse and manipulate
nanoscale objects, and could be used in
applications such as nanoparticle analysis and
water filtration. They are also of particular
interest in the sequencing of DNA. In a
typical experiment, a DNA molecule is
threaded through a nanoscale hole in a
membrane under an applied voltage, and
the ion current flowing through this pore is
monitored; when the DNA nucleotides enter
the pore they block the current by different
amounts, and this signal could then be used
to identify the individual bases and in turn the
DNAsequence.
The field of solid-state nanopores emerged
from work on Coulter counters1, ion channels
and protein pores25, and recently proof-ofprinciple DNA sequencing measurements
have been reported using ionic currents and
protein pores68. Compared with protein
nanopores, solid-state nanopores offer
potential advantages such as robustness, size
tunability and compatibility with large-scale
chip manufacturing. But solid-state nanopores
cannot yet be used to identify individual
bases. This is due, in part, to the fact that the
membranes used are too thick to probe the
local structure of the DNA; they are typically
silicon nitride membranes with thicknesses of
more than 10nm, which is equivalent to about
30DNA bases. As a result, researchers have
turned to thin membranes such as graphene,
which, because of its atomic thickness, could
potentially yield distinct current signals from
one or a few DNA bases.
In 2010, three independent research
groups led by Jene Golovchenko,
CeesDekker and myself reported
threading double-stranded DNA molecules
through nanopores in suspended graphene
membranes911 (Fig.1). Although there
were differences in the experiments such
as whether the graphene was grown9,11
or exfoliated12, and the diameters of the
nanopores used the underlying conclusions
were similar and showed that the ionic
currents could be used to detect the DNA.
In all three of these experiments, the DNA
passed through the nanopore too quickly for
individual bases to be resolved, and achieving
single-base resolution with graphene
nanopores remains an unresolved challenge.
The percentage of graphene nanopores
allowing DNA translocation is also lower than

Figure 1 | Top: Illustration of a single-stranded


DNA molecule passing through a graphene
nanopore. Bottom: Photograph of a solid-state
wafer with hundreds of nanopore chips, and
laboratory notebook entry9.

in typical silicon nitride nanopores, mostly


owing to wetting problems9. Furthermore,
more work is needed before graphene
nanopores will match the latest achievements
of traditional solid-state nanopores made
from silicon nitride1214 in terms of signal
level and signal-to-noise ratio. Nevertheless,
the work on graphene nanopores has already
inspired a search for other thin membrane
materials, and nanopores have, for example,
been created from hafnium oxide15,16,
molybdenum disulphide17 and boron
nitride18membranes.
For any solid-state nanopores be
it graphene, silicon nitride or something
else there is still a variety of fundamental
issues that need to be resolved before DNA
sequencing with ionic currents could
become a reality. For example, should
single- or double-stranded DNA be used?
Is a specific range of nanopore diameters
required, and how precisely will they have
to be manufactured? Improvements in the
nanopore devices will also be required. In
particular, current noise needs to be lowered

NATURE NANOTECHNOLOGY | VOL 9 | OCTOBER 2014 | www.nature.com/naturenanotechnology

2014 Macmillan Publishers Limited. All rights reserved

and signal-to-noise ratios increased at high


bandwidths19, or the translocation of the DNA
needs to be slowed down without more noise
being introduced into the signal. There are
also more prosaic but crucial details that need
to be dealt with: enough devices have to be
tested and reproduced by independent labs
to draw firm conclusions, a task that requires
skill, time and effort.
At this stage, it is not clear what solidstate nanopore material will be able to meet
all of these challenges or, in fact, whether
new nanopores will have to be developed
to achieve them. There is, however, no
theorem stating that only one material will
work. More likely, if one works out, others
may too although we should keep in
mind that, while it is encouraging that
protein pores have shown proof-of-principle
sequencing, this is not a proof that any of the
solid-state pores will work. And although
efforts were undertaken to commercialize
nanopores even before any proof-of-principle
sequencing demonstration existed, and it is
reasonable to extrapolate from existing data,
only reproducible experiments can prove
a hypothesis.

Marija Drndi is in the Department of Physics


and Astronomy, David Rittenhouse Laboratory,
University of Pennsylvania, Philadelphia,
Pennsylvania 19104, USA.
e-mail: [email protected]
References

1. Coulter, W.H. Means for counting particles suspended in a fluid.


US patent 2,656,508 (1953).
2. Kasianowicz, J.J., Brandin, E., Branton, D. & Deamer, D.W.
Proc.Natl Acad. Sci. USA 93, 1377013773 (1996).
3. Akeson, M., Branton, D., Kasianowicz, J.J., Brandin, E. &
Deamer, D.W. Biophys. J. 77, 32273233 (1999).
4. Deamer, D.W. & Akeson, M. Trends Biotechnol. 18, 147151 (2000).
5. Deamer, D.W. & Branton, D. Acc. Chem. Res. 35, 817825 (2002).
6. Cherf, G.M. et al. Nature Biotechnol. 30, 344348 (2012).
7. Manrao, E.A. et al. Nature Biotechnol. 30, 349353 (2012).
8. Laszlo, A.H. et al. Nature Biotechnol. 32, 829833 (2014).
9. Merchant, C.A. et al. Nano Lett. 10, 29152921 (2010).
10. Schneider, G.F. et al. Nano Lett. 10, 31633167 (2010).
11. Garaj, S. et al. Nature 467, 190193 (2010).
12. Wanunu, M. et al. Nature Nanotech. 5, 807814 (2010).
13. Venta, K. et al. ACS Nano 7, 46294636 (2013).
14. Carlsen, A.T., Zahid, O.K., Ruzicka, J., Taylor, E.W. & Hall, A.R.
ACS Nano 8, 47544760 (2014).
15. Shim, J., Rivera, J.A. & Bashir, R. Nanoscale
5, 1088710893 (2013).
16. Larkin, J. et al. ACS Nano 7, 1012110128 (2013).
17. Liu, K., Feng, J., Kis, A. & Radenovic, A. ACS Nano
8, 25042511 (2014).
18. Liu, S. et al. Adv. Mater. 25, 45494554 (2013).
19. Rosenstein, J.K., Wanunu, M., Merchant, C.A., Drndi, M. &
Shepard, K.L. Nature Methods 9, 487492 (2012).

743

FEATURE | FOCUS

Graphene devices for life


Kostas Kostarelos and Kostya S. Novoselov examine the potential of graphene in biomedical applications.

he use of nanomaterials in health


and life-science applications has been
steadily growing 1,2. Nanoscience could
allow the creation of new approaches in
medical intervention, and it promises to
revolutionize established clinical practice.
The design and engineering of delivery
vehicles for diagnostics or therapeutics
are just some examples among many;
others include point-of-care ultrasensitive
sensors, smart (responsive) substrates for
artificial tissue design and high-specificity
biomarkers. Graphene is considered the
archetypal nanostructure within the family
of carbon nanoforms, among fullerenes,
carbon nanotubes, nanohorns, graphene
quantum dots and others. Graphene
materials (GMs; a family of materials
including pristine graphene sheets, fewlayer graphene flakes, graphene oxide

and many others) offer a range of unique,


versatile and tunable properties that can be
creatively used for biomedical purposes.
Their lateral dimensions can be adjusted
between nanometres and millimetres, and
their thickness can be tuned from single to
hundreds of monolayers (also modulating
flexural rigidity). The two-dimensional
(2D) flat surface can be modified to
functionalize the surface character from
highly hydrophobic to patchy amphiphilic
to highly hydrophilic. The tunability of such
properties is perhaps unprecedented among
other nanomaterials, offering immense
design capabilities. Also important is that
graphene can be produced relatively cheaply
and in large amounts.
Graphene applications in biomedicine,
even though still in their infancy, can
be divided into several main areas:

transport (delivery) systems, sensors,


tissue engineering and biological agents
(for example antimicrobials). The use
of various carbon nanoforms in such
biomedical applications has been actively
pursued for the past decade or more3.
Therefore, determination of the unique
features offered by GMs (and other 2D
structures) is of critical importance in the
design and development of truly novel
constructs of enhanced or previously
unattainable functionality. Table1
illustrates how the most widely explored
nanocarbons (fullerenes and carbon
nanotubes) compare with graphene and
other 2D heterostructures in terms of their
biomedical applicability and potential. It
also highlights the numerous challenges that
each structure faces in implementation and
clinical adoption.

Table 1 | Opportunities and challenges in biomedical applications for different forms of nanocarbon.

Unique properties
used in biomedical
and life science

Fullerenes

Carbon nanotubes

Graphene materials

2D heterostructures

Free radical scavenging

Cylindrical shape
Photothermal capability
Inner space (for filling)

2D flat shape
Large available surface area
Flexibility
Electrical conductivity
Absence of bandgap
Aqueous solubility (in the case of
graphene oxide)
Versatility of chemical functionalization

Similar to graphene materials


in shape and structure
More variability in the mix
of physical properties from
different single layers

Molecular transporters
(drug delivery)
Near-infrared imaging agents

Highly sensitive biosensors


Molecular transporters
Coatings/substrates for tissue
engineering and implants

Almost no such applications


reported
Biosensing and biodetection
will be prime candidates

Biomedical application Antimicrobials


(most mature or
intensively explored)
Opportunity

Interaction with doubleTranslocation of biological


stranded nucleic acids (for membranes and barriers
example mitochondrial
DNA)

Responsive to a wide range of parameters


High sensitivity
Multiple read-out routes
Ease and speed of degradation

Fabricate-by-design based
on the selection of layers

Challenge

Aqueous dispersibility
Controlled manufacturing and
Non-specific DNA binding surface functionalization
leading to cytotoxicity
Aqueous dispersibility
Adverse (inflammatory)
responses related to fibre shape
Slow kinetics of biodegradation

Unknown cytotoxic limitations


Controllable dimensions
Determination of invivo biodegradability
kinetics

Interaction with biological


matter is currently unknown

744

NATURE NANOTECHNOLOGY | VOL 9 | OCTOBER 2014 | www.nature.com/naturenanotechnology

2014 Macmillan Publishers Limited. All rights reserved

FOCUS | FEATURE
So far, designs of delivery systems
based on GMs have primarily attempted
to make use of their very large surfaceto-volume ratio (larger than with
most other materials) and their facile
chemical modification. By careful tuning
of the dimensions and hydrophobic/
hydrophilic surface character of GMs,
one can potentially control their
capacity to translocate or interact with
different biological barriers (for example,
membranes or the glomerular filter). Also,
the razor-like shape of graphene sheets
can potentially help them to slide through
membranes and become internalized in
a cell. Some evidence of such capacity for
particular GM types has been reported4,
but there is still a lack of mechanistic
description of the way in which different
GMs interact with biological barriers.
It is also possible to consider the
graphene flake itself as a therapeutic agent.
Research efforts are currently focused on
exploring different GM types as local heat
sources activated on laser irradiation to
ablate tumour tissue by hyperthermia5.
The absence of a bandgap makes GMs
sensitive to irradiation across a wide spectral
range, therefore enhancing options for
the design of such agents. Antimicrobial
activity (bacteriostatic and bacteriolytic) is
another biomedical application that is based
on the inherent properties of GM sheets
themselves, even though there have been
contradicting reports about the inherent
antimicrobial activity of different GMs68.
For all therapeutic applications in which
administration of GMs is envisioned,
because the dimensions, surface chemistry
and hydrophilicity/hydrophobicity of
graphene flakes can vary widely, it will
be imperative to understand their impact
on some fundamental pharmacological
parameters (for example, blood circulation
kinetics, immune cell interactions and
responses, and tissue distribution) before

they can be tuned to achieve transport to a


specific location in the body.
Graphene-based sensor development is
another area of application being intensively
researched9. Because all graphene properties
are interlinked (for instance chemical
modification will change its electrical
resistance, and strain applied to it can
be directly detected through the Raman
spectrum), it could be possible not only
to sense a wide range of parameters, but
also to provide a large choice of read-out
methods (for instance, chemical doping
can be easily detected by transport, optical
or Raman measurements). Most promising
are the fast biological sensors with either
electrical or optical (plasmonic) readouts in which selectivity is ensured by
chemical functionalization. As graphene
simultaneously plays the role of a sensing
surface (which can be funtionalized to
increase selectivity) and the conducting
channel, its sensitivity can potentially be
very high (note that in many traditional
sensors based on field-effect transistors,
the conducting channel is separated from
the sensing surface)10. The other interesting
directions in the design of GM-based
devices include DNA sequencing through
nanopores11 and the use of graphene as a
photodetector or in plasmonic chemical
sensors12. The maturation and time-tomarket of graphene-containing biosensor
devices that will not require direct
administration into patients are expected to
be much more rapid than for administered
therapeutics or diagnostics.
Graphene has also been proposed
for coating or fabricating matrices and
substrates for the engineering of various
artificial tissue components and implants.
Some of the most promising are artificial
skin and orthopaedic implants13. Graphene
and graphene oxide membranes can also
be engineered in different thicknesses and
with different chemical functionalities

that could allow controllable permeation


of different molecules14. It is also
conceivable to impregnate graphenecontaining membranes with specific
(therapeutic) chemical species and release
themcontrollably 15,16.
It should be clear that all these biomedical
applications, although actively researched,
are still in the early stages of development. A
distinction in expectations should be made
among different types of device incorporating
GMs, mainly determined by the riskbenefit
ratio that each particular medical need and
application allows17.

Kostas Kostarelos and Kostya S. Novoselov are


at the National Graphene Institute, University
of Manchester, Oxford Road, Manchester
M13 9PL,UK. Kostas Kostarelos is also at the
Nanomedicine Lab, Faculty of Medical & Human
Sciences, University of Manchester, Manchester
M139PT, UK. Kostya S. Novoselov is also at
the School of Physics & Astronomy, University
of Manchester, Oxford Road, Manchester
M139PL,UK.
e-mail: [email protected];
[email protected]
References

1. Kostarelos, K. Nanomedicine 1, 13 (2006).


2. Wagner, V., Dullaart, A., Bock, A.K. & Zweck, A.
NatureBiotechnol. 24, 12111217 (2006).
3. Kostarelos, K., Bianco, A., Prato, M. Nature Nanotech.
4, 627633 (2009).
4. Li, Y.F. et al. Proc. Natl Acad. Sci. USA 110, 1229512300 (2013).
5. Zhang, W. et al. Biomaterials 32, 85558561 (2011).
6. Ruiz, O.N. et al. ACS Nano 5, 81008107 (2011).
7. Yang, X. et al. Nanoscale 6, 1012610133 (2014).
8. Liu, S.B. et al. ACS Nano 5, 69716980 (2011).
9. Novoselov, K.S. et al. Nature 490, 192200 (2012).
10. Hill, E.W., Vijayaragahvan, A. & Novoselov, K. IEEE Sensors J.
11,31613170 (2011).
11. Venkatesan, B.M. & Bashir, R. Nature Nanotech.
6, 615624 (2011).
12. Kravets, V.G. et al. Nature Mater. 12, 304309 (2013).
13. Yang, L., Zhang, L.J. & Webster, T.J. Nanomedicine
6, 12311244 (2011).
14. Joshi, R.K. et al. Science 343, 752754 (2014).
15. Servant, A. et al. Adv. Healthcare Mater. 3, 13341343 (2014).
16. Hong, J. et al. ACS Nano 6, 8188 (2012).
17. Kostarelos, K. & Novoselov, K.S. Science 344, 261263 (2014).

Graphene in the sky and beyond


Emilie J. Siochi explains how most of the properties of graphene could be of use in aerospace applications.

ith the premium placed on strong,


lightweight structures, carbon
materials have a long history of
use in aerospace applications. Graphitized
carbon and carboncarbon composites1
are used in thermal protection systems and
heat shields, carbon fibre composites are

used in aircraft 2, and more recently, carbon


nanotubes have been used on spacecraft 3.
As the newest member of this family of
materials, graphene also has interesting
properties that intersect with unique
aerospace requirements. Despite their many
attractive aspects, graphene-based structures

NATURE NANOTECHNOLOGY | VOL 9 | OCTOBER 2014 | www.nature.com/naturenanotechnology

2014 Macmillan Publishers Limited. All rights reserved

and systems, like any other material used in


aerospace, must clear a number of hurdles
before they will be accepted for use in
flight structures. Carbon fibre, for example,
underwent a development period of several
decades between initial discovery and largescale application in commercial aircraft 4.
745

FEATURE | FOCUS
a

Today

Future

Graphene oxide
nanocomposite as shielding

100 nm

Multifunctional structure with


embedded graphene electronics

Graphene oxide

Graphene sheet

Figure 1 | Notional applications of graphene in spacecraft. a, Different parts of a spacecraft could host
different types of application. b,d, A type of application available in the near term. Nanocomposites
(b) can be made out of graphene oxide (d) and used as charge dissipation layers. Scale bar in b,
40m. c,e, Future applications in which a graphene sheet (e) can be integrated in multifunctional
electronic components (c). Figures from: a, NASA/JPL-Caltech; b,d, Jae-Woo Kim, National Institute of
Aerospace/NASA Langley Research Center; c, Susanne Waltz, Lites/NASA Langley Research Center;
e, Nicholashan/Thinkstock.

One strategy for accelerating the


infusion of new material technologies into
aerospace applications is to evaluate the
near-, mid- and far-term uses that take
advantage of different graphene material
properties as they mature during the
development process (Fig.1). For example,
although the limited availability of pristine,
highly crystalline, single-layer graphene
currently constrains its use in electronics
to laboratory-scale devices, functionalized
graphene is available in commercial
quantities. Although some of the exotic
electronic transport properties are lost, it
retains enough conductivity to function
as an electrostatic charge dissipation layer
in space structures. To implement this
type of near-term application (Fig.1b,d),
the fabrication of nanocomposites
containing graphene oxide has to be
optimized and then the composites have
to be tested to establish if they can replace
materials currently used in electrostatic
charge dissipation layers. In the mid746

term, it would be feasible to envisage the


development of high-performance gasbarrier coatings using currently available
functionalized graphene. Loss of propellant
through boil-off from cryotanks used
for in-space propulsion is a significant
problem in long-duration missions5.
Proper dispersion of the two-dimensional
graphene nanoparticles in a composite
material could greatly reduce propellant
loss, as the diffusion path across the barrier
material would become so much more
tortuous. If the barrier properties exceeded
those of state-of-the-art materials based on
inorganic clay platelets, the mass reduction
could lead to adoption by vehicle designers.
Whereas both the near- and midterm applications described above are
achievable with functionalized graphene
nanocomposites whose performance can
readily be compared with state-of-the-art
materials, the far-term applications are
likely to revolve around electronics and
will, therefore, require advances in the

large-scale production of graphene sheets


with very high purity and crystallinity.
In particular, the atomic-layer thickness
of graphene, along with its mechanical
strength and high electron mobility,
suggests its suitability for flexible
electronics6. These devices are amenable
to being integrated in multifunctional
structures as depicted in Fig.1c,e.
Graphenes potential in this application
is broadened when used in combination
with MoS2, another rising star in twodimensional material systems7. The singlelayer atomic thickness of graphene has
the added benefit of providing intrinsic
radiation hardness8, which can significantly
reduce the required mass of conventional
radiation shielding material. As in the
near- and mid-term application examples,
the promise of improved performance and
reduced mass makes a case for further
research on graphene. In the far-term
case, truly revolutionary applications can
be envisaged, such as the integration of
embedded sensing in multifunctional
structures for smart aircraft and spacecraft.
In view of the variety of applications
described above, the broader needs of
aerospace technology summarized in
NASA technology development documents8
and the possible future uses described
in literature reviews9, graphene has the
potential to meet some critical needs in
the aerospace arena. Many challenges
must, however, be overcome to fully realize
its promise. One such barrier is the lack
of a large-scale method for reliably and
reproducibly producing high-quality
graphene. Laboratory-scale demonstrations,
although intriguing, are not sufficient
to warrant serious consideration in
aerospace systems. Maturing a new material
requires extensive development, testing,
qualification and certification before it can
be considered for use on flight vehicles.
This is typically done with material that is
available in large quantities with minimal
batch-to-batch variability in properties.
Engineers and designers of air and
space-flight vehicles are, sensibly, quite
conservative when it comes to adopting
new materials, as the environments to
which the material will be exposed can
be incredibly hostile. They must operate
reliably under exposure to both cryogenic
and extremely high temperatures, large
mechanical and vibrational loads, and
a spectrum of radiation. The inherent
risk imposed by these environmental
conditions and the large investments
made in these missions dictate the use of
only those materials that meet rigorous
qualification and certification standards.
Finally, with material selection decisions

NATURE NANOTECHNOLOGY | VOL 9 | OCTOBER 2014 | www.nature.com/naturenanotechnology

2014 Macmillan Publishers Limited. All rights reserved

FOCUS | FEATURE
typically made early in the design process,
the material development process has to
align with the time window of the mission
developmentschedule.
The examples of graphene applications
for aeronautics and space applications
described above are not intended to be
comprehensive. Rather, they provide some
hints of applications that, in the near
term, could enhance current technology
solutions, and, in the far term, could
enable revolutionary concepts not possible
today. Ultimately, the impact of graphene

in aerospace applications will depend on


reliable functionality, rather than novelty.
Emilie J.Siochi is at the NASA Langley Research
Center, Hampton, Virginia 23681, USA.
e-mail: [email protected]
References

1. Buckley, J.D. & Edie, D.D. (eds.) CarbonCarbon Materials and


Composites (Noyes, 1993).
2. Soutis, C. Prog. Aerospace Sci. 41, 143151 (2005).
3. Rawal, S., Brantley, J. & Karabudak, N. Proc. 6th Int. Conf.
Recent Advances in Space Technologies (RAST) 1319 (IEEE,
1214 June 2013).

NATURE NANOTECHNOLOGY | VOL 9 | OCTOBER 2014 | www.nature.com/naturenanotechnology

2014 Macmillan Publishers Limited. All rights reserved

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Acknowledgements

I thank my colleague K.E. Wise for his contributions to


this article.

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