COMMENTARY | FOCUS

The global growth of graphene

Wencai Ren and Hui-Ming Cheng
The large-scale production of graphene aimed at industrial applications has grown significantly in the
past few years, especially since many companies in China have entered the market.

G
raphene is the thinnest imaginable graphene sheets. This can be through direct from a metal substrate without sacrificing
material and is highly transparent; exfoliation in a liquid, with or without the it, so that it can be re-used, are two big
it is the strongest material ever use of a surfactant 8, or in the solid state by challenges for the CVD production of high-
examined, the most stretchable crystal, the edge functionalization9, or by first inserting performance, low-cost graphene TCFs.
most impermeable material, even to helium; a chemical species between the graphene
it has a record thermal conductivity 10 times layers in graphite to weaken their interaction Industrial production of small sheets
as high as copper, and the highest intrinsic followed by exfoliation10–12 (Fig. 1a). Bottom- Exfoliation of graphite is the most widely
electron mobility, about 100 times that up approaches such as substrate-free used method for the industrial production
of silicon1. Graphene has been discussed chemical vapour deposition (CVD) and of small graphene sheets (Table 1).
theoretically since the 1940s2, but it took solvothermal and combustion processes Angstron Materials in the United States and
60 years to experimentally obtain a few have also been developed. Depending on Thomas Swan in the United Kingdom are
sheets of micrometre-sized high-quality the strategy used, there are considerable two representative manufacturers that use
flakes weighing picograms3. Yet, only differences in yield, efficiency, cost, direct liquid-exfoliation methods to produce
10 years since Geim and Novoselov first accompanying pollution, ease of production high-quality pristine graphene materials.
used adhesive tape to isolate graphene and scalability of the manufacturing Thomas Swan’s first integrated process
from graphite, graphene sheets are being process, and in the morphology, structure producing kilogram quantities per day will
produced in hundreds of tonnes and tens of and properties of the products such as be up and running by September 201420.
thousands of square metres. thickness, lateral size, surface chemistry, Although this process is easy to realize
Five years ago, only a few USA- solubility, defect and impurity contents, and scale up (graphene materials can even
based small start-up companies, such as and electrical and thermal conductivities be produced using a kitchen blender 8), it
Angstron Materials, Vorbeck Materials and (Fig. 1 and Table 1). To produce uniform produces a mixture of small-size monolayer
XG Sciences, were making large volumes of monolayer and few-layer graphene sheets or few-layer graphene sheets and even thin
small graphene sheets4. Since then, tens of with high yield and high efficiency is a graphite flakes, and suffers from surfactant
graphene manufacturing companies have universal challenge for all these mass or organic solvent contamination.
sprung up all over the world, which produce production methods. China’s graphene manufacturers mostly
not only small graphene sheets but also Chemical assembly of small graphene use oxidation–exfoliation–reduction10,11
large-area, high-quality graphene films on an sheets and CVD are two methods to and intercalation–exfoliation12 methods to
industrial scale. In particular, the production produce large-area graphene films5,7,13–19 produce small graphene sheets. The Sixth
industry of graphene materials in China (Fig. 1b and Table 1). Chemical assembly Element (Changzhou) Materials and Tianjin
has been developing very rapidly, and its can be easily realized on various substrates Plannano Technology use oxidation to
total annual production capacity of small at low temperatures, but the films obtained form oxygen-containing functional groups
graphene sheets and graphene films exceeds suffer from poor quality, for example low covalently bonded with the graphene layer
400 tonnes and 110,000 m2, respectively. electrical conductivity 5,7,13. CVD produces to weaken the interlayer interaction of
high-quality graphene films by the catalytic graphite. Oxidation makes a dispersion of
Mass production methods of graphene decomposition of hydrocarbons on a metal graphite oxide difficult to handle and to
Small sheets and large-area films are two (for example, Cu, Ni, Pt or alloy) surface at clean, resulting in low efficiency; it also leads
major forms of graphene used for various high temperatures, and the films are then to severe structural damage to the graphene
applications. Small graphene sheets transferred to transparent substrates such layer and produces a lot of pollution. But
can be used in composites, functional as glass and polymers by etching away the the exfoliation of purified graphite oxide in
coatings, conductive inks, batteries and metal or by non-destructive electrochemical water by stirring and sonication produces a
supercapacitors5,6. Large-area graphene bubbling for transparent conductive film water-soluble functional material, graphene
films can be used as transparent electrodes (TCF) applications14–19. Roll-to-roll (R2R) oxide, which is easy to use for many
in touch panels, displays and photovoltaic CVD growth and transfer techniques have applications. The graphene oxide is usually
devices with potentially low cost, and been developed to fabricate large-area very thin and can be reduced to graphene,
more importantly, they are expected to TCFs16,17. Films produced over a large area, and defects and residual functional
be used in next-generation electronics however, usually show performance inferior groups in the reduced graphene oxide are
and optoelectronics such as flexible and to high-end indium tin oxide films but with beneficial for applications such as catalysis,
wearable devices6,7. higher cost. How to realize direct growth mechanically enhanced composites, and
Exfoliation of bulk graphite (the top- of large-area uniform defect-free few-layer composite electrodes in batteries and
down approach) is the most commonly used graphene films on arbitrary substrates, and supercapacitors. Sixth Element set up a
method for the mass production of small how to transfer the films intact and cleanly mass production line with a capacity of

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a • Liquid exfoliation

Pristine
Raw material: graphite
Sonication, shearing, graphene sheets
ball milling
NMP, GBL, DMEU, DMF, IPA
H2O + (sodium cholate, SDS,
SDBS, PVA)

• Solid exfoliation

Nearly pristine
Edge-functionalized graphene
graphene sheets
Thermal
Ball milling annealing
Dry ice, oxalic acid Ar, N2

• Oxidation–exfoliation–reduction

Graphite oxide Sonication, Graphene oxide, Reduced

stirring functionalized graphene Thermal annealing graphene oxide
(Modified) Hummers, H2O, NMP, DMF, Ar and/or H2, vacuum
Brodie, Staudenmaier ethanol, THF, PC Hydrothermal
NaNO3, KMnO4, H2SO4, Rapid heating, Chemical reaction
KClO3, HNO3 microwave, Hydrazine, NaBH4,
arc discharge hydrazine hydrate, alcohols
Ar, H2, air NaOH, KOH, VC, HI

• Intercalation–exfoliation

Intercalated graphite Expanded graphite Pristine

Heating, stirring, Heating, graphene sheets
electrochemical microwave Sonication

K, Cs, NaK2, K/THF, ClF3, Chemical reaction H2O + SDBS,

ICl, IBr, FeCl3, Li/PC, H2O, ethanol, H2O2, sodium cholate (aq.),
H2SO4, eutectic salt, CSA, TBA ethanol, NMP, pyridine,
H2O2, ionic liquids DMF, CSA, DSPE-mPEG

b
Small graphene sheets Large-area graphene films

Substrate CVD
Liquid exfoliation Large area
Intercalation–exfoliation Easy to realize Difficulty in growing large-area uniform
High yield Low yield, small size, quality multilayers on arbitrary substrates,
Usually thick, low concentration, and intact transfer from metals
non-uniformity non-uniformity,
impurities

Substrate-free
Solid exfoliation CVD
Quality

Easy to realize High purity

Agglomeration, Low yield,
non-uniformity low efficiency,
small size

Chemical reaction Oxidation– Assembly

Small size, exfoliation–reduction Low temperature,
low purity Easy to functionalize, easy to realize,
processable applicable for various
Low efficiency, substrates
serious pollution Low conductivity

Cost

Figure 1 | Main mass production methods of graphene. a, Four typical methods for the mass production of small graphene sheets by exfoliation of bulk graphite.
b, Comparison of the quality and cost of graphene products manufactured by different methods.

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COMMENTARY | FOCUS

Table 1 | Basic synthesis method, product, production capacity and main application products of several big graphene manufacturers.
Graphene Basic synthesis Basic product Production Main application products
manufacturer method capacity
Angstron Liquid exfoliation Pristine nanographene platelets 300 tonnes yr–1 Graphene/silicon anode materials
Materials Thickness: <100 nm
(USA) Carbon content: ≥95% (for product under three
layers in average thickness)
Thomas Swan Liquid exfoliation Graphene nanoplatelets kg day-1
(UK) Thickness: 5–7 layers (average) (September 2014)
Size: 0.5–2 μm
Sheet resistance: 10 ± 5 Ω per square (25-μm film,
equal to 27–80 S cm–1)
Impurity: ~8 wt%
Vorbeck Oxidation-thermal Functionalized graphene 40 tonnes yr–1 Conductive inks and coatings, graphene
Materials exfoliation Thickness: mostly 1–3 layers (October 2012) rubbers, flexible battery straps
(USA) Morphology: wrinkled
Sixth Element Oxidation–exfoliation– Graphene oxide, reduced graphene oxide 100 tonnes yr–1 Mechanical/thermally enhanced composites,
Materials reduction Thickness: ≤10 nm (November 2013) anticorrosion coatings
(China) Carbon content: ≥95%
Electrical conductivity: ≥2 S cm–1 (for electrical
conductive-type product)
XG Sciences Intercalation– Graphene nanoplatelets 80 tonnes yr–1 Graphene/silicon anode composite,
(USA) exfoliation Thickness: 2–15 nm (average) (August 2012) supercapacitor electrode materials,
Electrical and thermal conductivity: 3,800 S cm–1 and conductive inks and coatings, graphene
500 W mK–1, respectively (for 30-μm-thick graphene paper (for thermal spreading, and electrically
paper product) conductive applications, and so on)
Ningbo Morsh Intercalation– Graphene nanoplatelets 300 tonnes yr–1 Graphene conductive additives and
(China) expansion–exfoliation Average thickness: 3 nm (December 2013) graphene-coated current collector for lithium-
ion batteries, conductive inks, heat-radiating
coatings, anticorrosion coatings, thermally/
electrically conductive master batch
Deyang Intercalation– Graphene sheets (few-layer) 1.5 tonnes yr–1 Battery materials, thermal management
Carbonene expansion–exfoliation Thickness: ≤10 layers (October 2012) materials, conductive inks, conductive
Tech (China) Electrical conductivity: ~1,000 S cm–1 (for 300 tonnes yr–1 anticorrosion coatings
~15-μm-thick membrane) (2017–2019)
Bluestone CVD Graphene films on Cu, SiO2/Si, PET - Field-effect transistors, touch panels
Global Tech Film on PET: available maximum size 8 × 10 inch2,
(USA) <30 Ω per square at >85% transmittance (excluding
substrate), <800 Ω per square at 95% transmittance
(excluding substrate)
Film on SiO2/Si: available maximum size 4-inch wafer,
monolayer >95%, average Hall mobility:
2,000–4,000 cm2 V–1 s–1
2D Carbon CVD Graphene films on Cu, SiO2/Si, glass, PET 30,000 m2 Touch panels
Tech (China) Film on PET: available maximum size 450 × 550 mm2, (May 2013)
monolayer >90%, 200–400 Ω per square at >85% 200,000 m2
transmittance (including substrate) (December 2014)
Wuxi CVD Graphene films on Cu, PET 80,000 m2 Touch panels, touch sensors (5 million pieces,
Graphene Film Film on PET: ~600 Ω per square at >97% (December 2013) December 2013)
(China) transmittance (excluding substrate)
PowerBooster CVD Graphene films on Cu, PET - Touch panels
(China) Film on Cu: available maximum size 7.5 m2 (2013)
Film on PET: 50–140 Ω per square at 95.5%
transmittance

100 tonnes per year in 2013. The USA-based to produce high-quality pristine direct liquid-exfoliation route. However,
Vorbeck Materials uses similar technology graphene materials, which are suitable the product is usually thick. XG Sciences
to produce functionalized graphene with a for applications requiring high electrical reached an annual production capacity
unique wrinkled morphology 11. and thermal conductivity. This process of 80 tonnes in 2012, and its product has
Ningbo Morsh Technology, Deyang is easier to scale up and more efficient, an average thickness of ~2 to 15 nm. In
Carbonene Technology and XG Sciences causes less pollution than the oxidation 2013, Ningbo Morsh opened a production
are using non-oxidation intercalation route and has a much higher yield than the line with an annual output of 300 tonnes

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 FOCUS | COMMENTARY

a b Industrial production of large films

The United States and Korea pioneered
research on the CVD growth of graphene
films14–16. Together with China and
Japan, they are devoted to the industrial
production of graphene films in this way.
Bluestone Global Tech is a USA-based
CVD graphene manufacturer established
in 2011 that produces graphene films
on copper, SiO2/Si wafers and flexible
polyethylene terephthalate (PET), and its
largest film produced on copper that is
available is 24 × 300 inch2. Bae et al. from
Sungkyunkwan University in Korea first
reported16 an R2R production method to
produce large-area graphene TCFs 30 inches
across in collaboration with Samsung in
c d 2010. Today, several manufacturers of CVD-
grown graphene film and equipment, such
as Graphene Square, have been formed in
Korea. In 2012, Sony developed a new R2R
method17, which directly applied a current
to heat a copper foil instead of using the
traditional heating method14–16,18,19, and
realized the production of graphene films
more than 100 m in length.
Although its research on graphene
100 nm 1 nm
produced by CVD is a little behind the
United States and Korea, China has made
Figure 2 | Mass production and application of small graphene sheets. a, A shipment of few-layer graphene some important contributions such as
product manufactured by Deyang Carbonene Technology. b, Graphene-coated aluminium current the growth of large single crystals18, pure
collectors for lithium ion batteries. c,d, Transmission electron micrograph (c) and aberration-corrected monolayers19, three-dimensional graphene
high-resolution transmission electron micrograph (d) of the product in a, showing its very high quality. networks21, and the non-destructive
Images: a, © Deyang Carbonene Technology; b, courtesy of Songfeng Pei; c,d, courtesy of Zhibo Liu. electrochemical bubbling transfer
method18 that has already been used by
some manufacturers. As potentially the
of graphene sheets with an average impermeability, small graphene sheets biggest market for smart phones and one
thickness of 3 nm. Deyang Carbonene uses have also been explored as antistatic and of the largest touch-panel manufacturing
a proprietary intercalation–expansion– anticorrosion coatings. Developing thermal countries, the industrial production of large-
exfoliation technique12 and produces high- interfacial or heat-spreading materials area graphene films in China has developed
quality pristine graphene sheets of fewer that make use of graphene’s high thermal very rapidly in the past 3 years. In January
than 10 layers with a yield over 90 wt% conductivity in electronics such as in mobile 2012, 2D Carbon Tech announced the first
and high electrical conductivity more than phones and light-emitting diodes is another capacitive touch panel in the world based
1,000 S cm–1 (Fig. 2). A pilot production application focus in China. on graphene. In May 2013, it launched its
line with a capacity of 1.5 tonnes per year
has been operating since October 2012, and a b
a production line of 100 tonnes per year is
under construction.
Compared with mass production, the
applications of small graphene sheets
are still at an early stage. Almost every
graphene manufacturing company has been
attempting to use these materials for many
purposes, ranging from energy storage,
composites and functional coatings to
© 2D CARBON TECH

electronics (Table 1). As China is one of the

biggest lithium-ion battery manufacturing
countries, in China lithium-ion batteries
are the most explored application of small
graphene sheets where graphene has been
mainly used as a conductive additive
in electrodes or as current-collector Figure 3 | Mass production and application of large-area graphene films. a, A large transparent conductive
coatings. Because of their two-dimensional graphene film (about 20 × 20 cm2) manufactured by 2D Carbon Tech. b, Prototype of a mobile phone
structure, high electrical conductivity and (2D Carbon Tech) using a graphene touch panel.

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COMMENTARY | FOCUS

first commercial line, with a capacity of substrates at low temperatures, and the Academy of Sciences, Shenyang 110016, China.
30,000 m2 graphene films per year (Fig. 3), efficient, intact and clean transfer from metal e-mail: [email protected]; [email protected]
and the company is planning to reach substrates without sacrificing the metals so
200,000 m2 by the end of 2014. In December that they can be re-used are still challenges References
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big problem. Improving the controllability appropriate uses for the material. ❐ Acknowledgements
of mass production techniques to produce We thank S. F. Pei, L. P. Ma and H. Bi for discussions,
L. C. Yin for help with drawing the structural models in
uniform graphene sheets, realizing direct Wencai Ren and Hui-Ming Cheng are at the Fig. 1a, and NSFC (Nos. 51325205, 51290273, 51221264 and
growth of large-area, uniform, defect-free, Shenyang National Laboratory for Materials 51172240), MOST of China (No. 2012AA030303) and CAS
few-layer graphene films on arbitrary Science, Institute of Metal Research, Chinese (No. KGZD-EW-303-1) for support.

Challenges and opportunities

in graphene commercialization
Amaia Zurutuza and Claudio Marinelli
As technical knowledge, manufacturing methods and the development of applications mature, key
factors will affect the pace of commercialization of graphene.

I
t is now 10 years since the Nobel given at Graphene: Commercialisation significant expansion and revenue increase.
Prize winners Andre Geim and and Applications, Univ. of Manchester, An increase in graphene demand should
Konstantin Novoselov published the first 1 12–13 June 2014) and a range of these drive up production scale and drive down
of a series of seminal papers that triggered a materials commercially available. costs, resulting in a shift from material sales
sharp rise in the level of graphene research Nevertheless, there are only a few to a market dominated by sales of graphene-
efforts worldwide. Fuelled by public (for graphene-based products that have reached based components, systems and products.
example, European Commission, UK and the market, such as the tennis racket by The steep rise in graphene application
Korean governments) as well as private Head, the battery strap by Vorbeck, the oil- patents further supports the realization of an
investments (for example, Samsung, drilling mud by Nanochem or the phone industrial graphene market in the upcoming
IBM, Nokia), research on graphene has touch screen by Samsung. These products years3. Figure 1 shows the comparison of the
produced a substantial body of scientific represent an initial market entry rather than patent landscape of different materials. The
knowledge, accompanied by a surge of the first, full commercial wave of graphene number of graphene patents has increased
publications and patent applications. The products. The size of the graphene market significantly more steeply than for the other
past 6–7 years have seen a steady, worldwide was estimated2 to be around US$12 million benchmark materials, including silicon
emergence of private ventures focused on in 2013, indicating that so far we are still in a (Fig. 1, inset).
the manufacturing and commercialization phase of research and development, in which Progress in the commercialization of
of graphene and graphene-based materials, the market is dominated by sales of raw graphene can be assessed by looking at
with 44 companies currently active graphene materials. The market projections the growth of demand-driven graphene
(Mark Rahn from MTI Venture, talk for the next 5–10 years, however, indicate production (rather than production capacity)

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