feature

Selling graphene by the ton

Michael Segal
Small start-up companies are making large volumes of graphene, the worlds thinnest material, for applications
such as composites and electrodes.

The graphene is already

there all you have to do
is peel it off.
Bor Jang, Angstron Materials.

At present, three small US companies

account for the bulk of graphene
manufacturing capacity: Angstron
Materials; Vorbeck Materials in Jessup,
Maryland; and XG Sciences in East
Lansing, Michigan. The companies take the
same basic manufacturing approach, which
is to break apart graphite into the sheets
of graphene that make it up usually
by intercalating acids between them. The
resulting intermediate is then thermally or
mechanically treated to extract graphene
platelets (or nanoplatelets). These platelets
can consist of a single layer or multiple
layers of graphene, and measure hundreds
of nanometres to tens of microns across.
612

VorBeck MATeriAlS

raphene is, by any measure, a

story of extremes. Consisting of
a few sheets of carbon atoms, it is
the strongest material ever measured1,
it has a thermal conductivity more than
double that of diamond2 and has a charge
mobility that is among the highest of any
semiconductor3. But just as remarkable
has been the speed at which this material
has moved from the research laboratory to
the marketplace.
The exceptional electrical properties of
graphene were discovered only five years
ago in experiments that involved manually
peeling samples weighing picograms from
bulk graphite4. Today the total production
output of various flavours of graphene
exceeds 15 tons per year, produced in
more than 40,000 square feet of facilities,
and this is set to increase to more than
200 tons per year within the next year
or two. We actually have a company
asking the question right now, When
will I get 5 tons? says Bor Jang, the chief
executive officer of Angstron Materials,
which is based in Dayton, Ohio. We cant
produce enough.

A shipment of Vorx a functionalized graphene

manufactured by Vorbeck Materials ready to
be sent to a development partner.

The use of acids can lead to oxidation of

the graphite, and Vorbeck has licensed
an approach developed at Princeton
University5,6 to convert graphite oxide into
graphene. Angstron, meanwhile, has also
developed a process that avoids chemical
intercalation and oxidation altogether.
These approaches have the common
advantage of being inexpensive. The low
cost results from a relatively simple and
low-energy treatment process, and a cheap
starting material: graphite is mined and
sold at a cost of cents per gram. Jang puts
it simply: The graphene is already there
all you have to do is peel it off.

What is graphene good for?

Although much of the early excitement

around graphene centred on its
semiconducting properties and exotic
physics, the tons of material now being

manufactured will not end up in advanced

devices such as transistors. Instead, most
applications fall into two broad and not
always exclusive categories: composites
and electrodes. Composites consist of
graphene dispersed into a host matrix,
and take on some of the properties of
graphene as a result. These may include
strength, stiffness, and electrical or thermal
conductivity. For example, some containers
used to store and transport volatile fuels are
made from polymer or rubber composites.
Incorporating graphene would increase
their stiffness by an order of magnitude,
and allow them to conduct electrical
currents, reducing the probability of
electrical discharges and increasing safety.
Similarly, packaging made from
a graphene composite could shield
electronics from radio frequency signals,
conduct current to external devices or even
store information. Vorbeck is focusing
on printable conductive inks (a distinct
class of composites), for applications in
printed electronics such as radio-frequency
identification tags, low-resolution displays
and backlights, sensors, flexible connectors
and packaging. Graphene makes these inks
both highly conductive and easy to process.
Graphene-based electrodes take
advantage of the materials electrical
conductivity, transparency and
surface area. One attractive target is
the replacement of indium tin oxide,
which is used in LCD displays and
photovoltaic devices. Graphene offers
easier processing and, potentially, much
lower costs. Shortages of indium have
driven up its cost from 10 cents per gram
in 2002 to about 60 cents per gram today,
after reaching a peak of one dollar per
gram in 2007. Another target is energy
storage, potentially replacing the graphite
electrodes found in batteries, capacitors
and fuel cells. If you have an inexpensive
graphene nanoplatelet material and can
control its concentration, orientation,
surface chemistry and so on, it has the
potential for making a significant impact
on performance, says Lawrence Drzal,
chief scientist of XG Sciences and professor

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feature

chemists and physicists look

at the properties of a single
graphene sheet, whereas
engineers look at an assembly
of graphene or other
nanoparticles into a device.
lawrence Drzal, XG Sciences.

Although these applications have

attracted the undivided attention of startup companies, larger chemical companies
like Dow, 3M, BASF and DuPont
have so far taken a more conservative
approach. BASF has, for example, formed
a partnership with Vorbeck to jointly
develop products. Dow, on the other hand,
has investigated graphene for over five
years, but remains unconvinced about its
prospects. The company initially focused
on cable-shielding applications, but costs
proved to be uncompetitive. Ive yet to
see applications that are really demanding
large quantities of these products and
thats a concern both for graphene and for
carbon nanotubes, although we recognize
that much of the development is still
early-stage, says Steve Hahn, a senior
scientist with Dows Ventures and Business
Development division.
The discrepancy between the
enthusiasm of the start-up companies

and the conservatism of their larger

counterparts is partly a matter of scale.
Even though tens of tons is orders of
magnitude beyond laboratory production
scales, it is also orders of magnitude below
industrial chemical company scales. Wed
consider a few tons per year to be a pretty
small volume of material compared with
what we typically manufacture, says
Hahn. Dow would probably need to
see a bigger opportunity for it to make
economic sense.
At the other end of the market are
start-up companies serving pristine,
single-layer or few-layer graphene in small
quantities for research into fundamental
science as well as applications that are
further from commercialization, such as
graphene-based transistors. For example,
Graphene Industries, a company spun
out of Andre Geims group at Manchester
University7, sells individually characterized
flakes one at a time. This part of the market
may also soon be served by chemical
vapour deposition techniques, which
produce large-area and high-quality
graphene8, but these samples are likely to
be expensive relative to graphite-derived
graphene in the near term.

What is graphene?

Although the International Union of Pure

and Applied Chemistry (IUPAC) defines
graphene as a single layer of carbon atoms,
researchers routinely talk of bilayer, trilayer
and multilayer graphene. Industry stretches
the definition further still, to include any
highly exfoliated graphite product. Vorbeck
uses predominantly single-layer graphene

in its composites, and two or three tons

of Angstrons production capacity will be
devoted to single-layer graphene. However,
about a fifth of Angstrons output will be
30-layer graphene, and XGs nanoplatelets
are typically 5 nm thick, corresponding
to more than 16 layers of graphene. Hahn
says that Dow is still working through
the process of exactly what it means to call
something graphene.
Part of this process involves developing
metrics that allow a quantitative
description of a particular graphene or
graphene composite sample. The most
common metrics are specific surface area,
in units of area per mass, and thermal
and electrical conductivity. Single-layer
graphene has a specific surface area of
approximately 2,600 m2 g1, whereas the
best samples produced by industry have
values between 1,000 and 1,800 m2 g1, even
those that are characterized by electron
microscopy as being single layer. This is
due in part to the agglomeration of the
material when it is assembled into a bulk
sample, device or composite. Similarly,
the thermal conductivity of a single sheet
of graphene has been measured to be
4,000 W m1 K1 (ref. 2), which is three
orders of magnitude greater than that of the
typical graphene composite.
I make the distinction that chemists
and physicists look at the properties of a
single graphene sheet, whereas engineers
look at an assembly of graphene or other
nanoparticles into a device, says Drzal. The
method used to manufacture a composite
material or device, therefore, is as
important as the properties of the graphene

AnGsTROn MATERiALs

of chemical engineering and materials

science at Michigan State University. We
are spending more effort in developing
new applications in energy storage than
anything else, says Jang.
Energy applications are at the core of
another young company, Graphene Energy,
Inc., spun out of Rod Ruoff s laboratory at
the University of Texas at Austin. Graphene
Energy is focusing on ultracapacitors, which
fill a niche between the high-energy/lowpower densities of batteries, and the highpower/low-energy densities of standard
dielectric capacitors. Ultracapacitors require
a conductive and high surface area electrode,
and graphene fits the bill. There is reason
to believe that the specific capacitance could
be improved significantly, by a factor of two
or three, says Ruoff. This would be, for
many people, absolutely game-changing.
Although Graphene Energy is agnostic
about whether it will manufacture its own
graphene or purchase it from an external
supplier, it will need large volumes of the
material: To have a long-range impact
in ultracapacitors youre going to need
thousands to tens of thousands of metric
tons per year, says Ruoff.

A fuel cell bipolar plate manufactured by Angstron. The compressionmoulded thermoplastic composite
contains 60% graphene by weight.

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2009 Macmillan Publishers Limited. All rights reserved

613

feature
used. This fact, combined with the variety
of metrics appropriate for different devices
and materials, means adherence to a
strict single-layer definition is not useful.
Instead, industrial researchers focus on
what is good enough for their application.
At Dow, Hahn has settled on a surface
area figure of 500 m2 g1, which he calls a
bit of a benchmark. And researchers at
Graphene Energy have achieved what they
call excellent ultracapacitor performance
using electrodes with surface areas between
400 and 700 m2 g1, which is well below the
theoretical maximum for graphene.

i think graphene is now ready

for commercialization.
John lettow, Vorbeck.

Industry has extended not only the

definition of graphene, but also its history,
questioning the claim that it is a new
material. The original synthetic work for
graphene goes back into the late 1800s,
says Hahn. It is hard to look at graphene
and say it is a new material. This early
work focused on intercalated or lamellar
compounds of graphite, and by 1970 singlelayer graphene on nickel substrates, called
monolayer graphite, had been isolated9,10.
In the 1980s, Union Carbide was producing
graphite particles under the trade name
Grafoil, with surface areas of 20 m2 g1,
roughly the surface area of what might
today be called 100-layer graphene11.
While Angstron, XG and Vorbeck
have all applied for patent protection of
their own fabrication approaches, this
long history complicates the securing
of such rights. If manufacturers just
use intercalation and exfoliation, the
intellectual property is not very defensible,
says Jang. Another way to do it is to patent
the applications.
Intellectual property protection by
patents is therefore supplemented by the
development of in-house, equipmentspecific know-how, particularly related
to questions of scaling and efficiency.
Anybody could probably go into a
laboratory and generate this material at the
one gram level, says Drzal. But scaling
up the process to the point where youre
going to make significant quantities is
a challenge.

that other carbon nanomaterial

In addition to competing with established

materials such as graphite and metallic

614

inks, graphene also competes with

its close older relative, the carbon
nanotube. In almost all of the areas
that we are developing with our initial
customers, they have definitely evaluated
nanotubes, says John Lettow, president
of Vorbeck. Thats been step one in the
process. Big companies like Bayer and
Showa Denko are already producing
hundreds of tons of nanotubes per year,
with plans to produce thousands of tons in
the near term.
In competing with nanotubes, graphene
makers point to cost, surface area, ease of
processing and, possibly, safety as its main
advantages. The cost advantage derives
from the process: nanotube synthesis
usually requires a higher energy input,
a high-purity gaseous feedstock and
catalysts. I think theres a perception
that graphene might in the long run be
a pretty inexpensive commodity-type
material compared with carbon nanotubes,
says Ruoff.
The remaining advantages largely
derive from geometry. The fact that about
half the surface area of a nanotube is
relatively inaccessible (because it is inside
the nanotube) is a critical drawback
for ultracapacitors and other energy
applications. Graphenes planar geometry
reduces tangling and clumping relative to
nanotubes, says Lettow, and leads to films
with lower resistances.

Graphene might in
the long run be a pretty
inexpensive commoditytype material compared with
carbon nanotubes.
rod ruoff, Graphene energy.

This difference in geometry may also

lead to a safety advantage for graphene.
The interesting thing about graphene
nanoplatelets is that they are nano in
one dimension rather than three, says
Drzal. This may mean that it less likely to
move through biological barriers. From
everything weve seen so far, potentially
theres much less of a health risk associated
with it. Both Drzal and Jang believe that
handling requirements for graphene will
be similar to that for coal dust and other
small particles.
For Jang, the combination of cost and
a reduced health risk is a compelling

one: Graphene will gradually replace

nanotubes in many applications, he
says. Indeed, Angstrons literature claims
that graphene trumps nanotubes on a
number of other fronts: purity, ease of
functionalization, thermal conductivity,
impact on viscosity, uniformity of
dispersion, loading, barrier properties and
capital investment.

Past and future

Graphene manufacturers believe that

they have solved many of the technical
challenges involved in high-volume
production, and consider the material
that they are now producing as ready for a
variety of applications: I think graphene
is now ready for commercialization, says
Lettow. In their view a more important
challenge is to ensure that real applications
are developed in time to provide the
demand for these high volumes. In the past
many companies making nanomaterials
have often focused on volume manufacture
before applications were mature, leading
to a number of them consuming large
amounts of cash, and then going bankrupt.
That lesson is very well learnt from carbon
nanotubes, says Lettow.
The graphene start-up companies
discussed here have, so far, spent only a
small fraction of the money that was spent
by high-volume nanotube manufacturers
over the equivalent period. Moreover, they
are moving quickly towards marketable
products by maintaining close relationships
with development partners, which are
absorbing the majority of their production
output. When single development partners
are buying tens of kilograms and putting
it into composites at 2% or 10% loading,
their production of pilot products is in the
tons, says Jang. Next year you will see
a breakthrough.

Michael Segal is an Associate Editor for

Nature Nanotechnology.
references
1. Lee, C., Wei, X., Kysar, J. W. & Hone, J. Science
321, 385388 (2008).
2. Balandin, A. A. et al. Nano Lett. 8, 902907 (2008).
3. Chen, J.-H., Jang, C., Xiao, S., Ishigami, M. & Fuhrer, M. S.
Nature Nanotech. 3, 206209 (2008).
4. Novoselov, K. S. et al. Science 306, 666669 (2004).
5. Li, J.-L. et al. Phys. Rev. Lett. 96, 176101 (2006).
6. Schniepp, H. et al. J. Phys. Chem. 110, 85358539 (2006).
7. Nature Nanotech. 3, 523 (2008).
8. Obraztsov, A. N. Nature Nanotech. 4, 212213 (2008).
9. Eizenberg, M. & Blakely, J. M. Surf. Sci. 82, 228236 (1970).
10. Park, S. & Ruoff, R. S. Nature Nanotech. 4, 217224 (2009).
11. Chung, D. D. L. J. Mater. Sci. 22, 41904198 (1987).

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2009 Macmillan Publishers Limited. All rights reserved