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DOI: 10.1002/adma.200800757

Mechanically Strong, Electrically Conductive, and


Biocompatible Graphene Paper**
By Haiqun Chen, Marc B. Müller, Kerry J. Gilmore, Gordon G. Wallace,* and Dan Li*

Research on graphene was originally motivated by its buckypaper and GO papers.[4,17,18] Here, we demonstrate that
peculiar electrical transport properties and the promise of the resulting graphene paper displays a remarkable combina-
future applications in nanoelectronics.[1,2] Graphene sheets, tion of thermal, mechanical, and electrical properties, whilst
owing to their exceptional thermal and mechanical properties preliminary cytotoxicity tests suggest biocompatibility, making
and high electrical conductivity, are also of great interest to this new material attractive for many potential applications.
serve as new nanoscale building blocks to create unique Graphene dispersions were prepared by controlled reduc-
macroscopic materials.[3–5] Recent studies have shown that tion of GO dispersions with hydrazine using the procedure
graphene sheets can be prepared in large quantity through reported in one of our recent publications.[12] Graphene paper
chemical conversion from graphite,[6–12] which has facilitated was then fabricated by filtration of a measured amount of
the fabrication of graphene-based electronic devices[13,14] and graphene dispersion through an Anodisc membrane filter,
has also made it possible to create new bulk materials followed by air drying and peeling from the filter. The samples
comprising graphene sheets for a broader range of applica- of graphene paper were annealed at different temperatures
tions.[3–5,15,16] For example, it has been recently demonstrated before being cooled to room temperature for various
that chemically modified graphene sheets can be dispersed measurements (see the Experimental section for details).
throughout a polymeric[3] or inorganic matrix[15] to make We observe that as-prepared graphene paper displays a
electrically conducting composites with a percolation threshold shiny metallic luster on both sides (Fig. 1A). Scanning electron
as low as 0.1 vol %. Thin graphene films have also been used as microscopy (SEM) analysis reveals that the surface of the
potential transparent electrodes for solar cells.[16] More graphene paper is quite smooth (Fig. 1B) and the fracture
recently, Ruoff and co-workers have demonstrated that graph- edges of the papers exhibit a layered structure through the
ene oxide (GO) sheets dispersed in water can be assembled into entire cross-section (Fig. 1C and D), which looks similar to the
a well-ordered structure under a directional flow, yielding microstructure obtained for GO paper prepared using the
ultrastrong GO paper.[4] GO paper is superior to many other same method.[4] These results indicate that, similar to
paperlike materials in stiffness and strength, however, a lack of hydrophilic GO sheets,[4] chemically reduced graphene sheets
electrical conductivity limits its use. Although GO paper can can also be assembled to form highly ordered macroscopic
be rendered conductive by thermal annealing, the structure structures under vacuum filtration-induced directional flow.
and mechanical properties seriously deteriorate after this The thickness of the graphene paper can be varied from tens of
treatment (see below for further discussion). nanometers to around 10 mm by adjusting the volume of the
We have recently demonstrated that aqueous dispersions of colloidal dispersion. Nevertheless, only stable and agglomer-
graphene sheets can be readily produced without the need for ate-free graphene colloids can produce uniform, smooth, and
polymeric or surfactant stabilizers.[12] This has enabled us to shiny paper. In contrast to GO paper,[4] graphene paper cannot
prepare electrically conductive graphene paper directly, using be redispersed into water by ultrasonication, exhibiting an
the same strategy that has been used to make carbon nanotube excellent water-resistance behavior.
Another remarkable property of graphene paper is its high
thermal stability, especially when compared with GO using
[*] Dr. D. Li, Prof. G. G. Wallace, Dr. H. Chen, M. B. Müller, thermogravimetric analysis (TGA) (Fig. 2A). The mass loss
Dr. K. J. Gilmore
ARC Centre of Excellence for Electromaterials Science below 200 8C can be attributed to the evaporation of adsorbed
Intelligent Polymer Research Institute water. A slight mass loss appears between 200 and 500 8C,
University of Wollongong presumably owing to the decomposition of some residual
Northfields Avenue, Wollongong, NSW 2522 (Australia)
E-mail: gwallace@uow.edu.au; danli@uow.edu.au
oxygen-containing groups. In contrast to GO paper (Fig. S1A
Dr. H. Chen of the Supporting Information), there is no sharp weight loss at
Department of Safety and Environment Engineering around 200 8C for graphene paper, indicating that most
Jiangsu Polytechnic University oxygen-containing groups have been removed by the hydra-
Changzhou 213016 (PR China)
zine reduction. The total weight loss (<10%) of graphene
[**] D.L. and G.G.W. acknowledge the support from the Australian paper between 200 and 500 8C is much lower than that of GO
Research Council. H.C. acknowledges the support from the Jiangsu
Province Studying-Abroad Foundation. Supporting Information is paper (ca. 30% loss, as shown in Figure S1A of the Supporting
available online from Wiley InterScience or from the authors. Information). When graphene paper is annealed between 200

Adv. Mater. 2008, 20, 3557–3561 ß 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim 3557
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graphene paper is slightly greater than,


but quite close to, that of graphene layers
in pristine natural graphite, indicating that
chemically prepared graphene sheets are
similar to the pristine sheets. The slightly
increased d-spacing of chemically pre-
pared graphene paper can be ascribed to
the presence of a small amount of residual
oxygen-containing functional groups or
other structural defects.
As a consequence of better ordering
and additional deoxygenation by thermal
annealing, the electrical conductivity of
graphene paper is found to increase with
treatment temperature (Fig. 2C). It is
noteworthy that although GO can be con-
verted to conductive graphene by thermal
deoxygenation, the electrical conductivity
of thermally treated GO paper is found to
be lower than that of our graphene paper,
most likely owing to the disrupted struc-
ture of heat-treated GO (Fig. S1C and D
of the Supporting Information). For
example, the conductivity of GO paper
heat-treated at 220 and 500 8C is around
0.8 and 59 S cm1, respectively, while the
graphene paper treated at the same
temperatures exhibits a conductivity of
118 and 351 S cm1, respectively. The
Figure 1. A) Photograph of two pieces of free-standing graphene paper fabricated by vacuum
conductivity of the graphene paper sam-
filtration of chemically prepared graphene dispersions, followed by air drying and peeling off the
membrane. Front and back surfaces shown. B) Top-view SEM image of a graphene paper sample ple treated at 500 8C is an order of
showing the smooth surface. C,D) Side-view SEM images of a ca. 6 mm thick sample at increasing magnitude higher than that reported for
magnification. compressed pristine graphite powder,
again indicative of a strong intersheet
interaction in the graphene paper.[6]
and 500 8C, the mechanical integrity of the paper as well as the Similar to GO prepared using the same method,[4] graphene
physical appearance (smooth shiny surface) are retained. In paper is supposed to be formed by stacking and interlocking of
fact, the lustrous appearance is enhanced by thermal annealing. individual sheets under a filtration-induced directional flow.
In contrast, when GO paper is treated above 200 8C, the paper Given that individual graphene sheets are predicted to have a
becomes crumpled (Fig. S1B and C of Supporting Informa- tensile modulus of up to 1.01 TPa[9] and the sheets are
tion), presumably as a result of vigorous gas release caused by well-packed in graphene paper, we surmised that similar to GO
thermal decomposition.[6] These results clearly indicate that paper, graphene paper should have excellent mechanical
paper composed of chemically reduced graphene is much more properties. Mechanical analysis of the graphene paper reveals
thermally stable than unreduced GO paper. that the stiffness and tensile strength are comparable to or, if
We have further studied the effect of thermal annealing on properly annealed, higher than those of GO paper. Figure 3A
the microstructural ordering of graphene sheets in the resulting presents typical stress–strain curves of graphene paper
paper using X-ray diffraction. As shown in Figure 2B, annealed at various temperatures. The results obtained using
as-filtrated graphene paper, when dried at room temperature, the samples dried at room temperature show an elastic and a
displays a weak and broad X-ray diffraction peak at around plastic deformation region as well as an initial straightening
238, corresponding to a layer-to-layer distance (d-spacing) of region similar to those observed for GO paper.[4] When the
about 0.387 nm. As the annealing temperature is increased, the samples are annealed at temperatures above 100 8C, the plastic
peak at around 238 becomes more pronounced and sharper. deformation is difficult to observe (Fig. 3A). The stiffness and
The d-spacing is slightly reduced, approaching 0.341 nm when strength of graphene paper samples are found to be dependent
treated at 500 8C. The XRD results clearly indicate that on the thermal annealing temperature used. As shown in
thermal annealing enables a better ordering of the two- Figure 2B and C, both stiffness and strength increase with
dimensional sheets. Note that the d-spacing of the resulting increasing annealing temperature up to about 220 8C. The

3558 www.advmat.de ß 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim Adv. Mater. 2008, 20, 3557–3561
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Figure 3. A) Typical stress–strain curves, B) Young’s modulus, and
C) tensile strength of graphene paper strips that have been heat-treated
at various temperatures. The mechanical properties of GO paper are also
presented in (B) and (C) for comparison. The data shown in (B) and (C) are
Figure 2. A) Normalized remaining mass of graphene paper as a function
averages of six measurements.
of temperature in air and argon gas, respectively. B) XRD patterns of
graphene paper samples that have been heat treated at various tempera-
tures. For comparison, the XRD pattern of the pristine graphite powder is
included. All the XRD patterns were recorded at room temperature. of individual sheets (likely owing to the weaker bonding
C) Room-temperature electrical conductivity of graphene samples that between sheets), they are both higher than those of GO paper
have been thermally annealed at various temperatures.
and over 10 times higher than the corresponding values for
flexible graphite foils.[4,19,20] To our knowledge, these values
are the highest yet reported for electrically conducting
enhancement of mechanical properties is attributed to the carbon-based paperlike materials. When the heat treatment
better ordering of graphene stacks brought about by thermal is performed at temperatures above 220 8C, the graphene paper
annealing, which results in enhanced interlayer contact and becomes more brittle and the measured stiffness and strength
interactions of graphene sheets. This is consistent with the tend to decrease with annealing temperature. Further studies
XRD and electrical conductivity measurement results. The are required to understand this phenomenon.
sample annealed at 220 8C yields the greatest mean Young’s Note that for GO paper samples, the mechanical properties
modulus at 41.8 GPa, and the greatest mean tensile strength at are comparable to those of graphene paper when thermally
293.3 MPa. Although the values are still much lower than those annealed below 150 8C. However, both stiffness and strength

Adv. Mater. 2008, 20, 3557–3561 ß 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim www.advmat.de 3559
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Experimental
Fabrication of Graphene Paper: Graphene paper was fabricated by
vacuum filtration of graphene dispersions. In a typical procedure,
graphite oxide was synthesized from natural graphite powder (SP-1,
Bay Carbon, Bay City, MI, USA) using a modified Hummers method
[27, 28]. After being purified by filtration and subsequent dialysis or by
several runs of centrifugation/washing, graphite oxide was exfoliated
into water by ultrasonication for 30 min using a Branson Digital
Sonifier (S450D, 500 W, 30% amplitude). The obtained GO was
diluted to 0.25 mg mL1. With the pH of the dispersion adjusted to 10
using ammonia and the solution surface covered with a thin layer of
mineral oil, the dispersion was then subjected to reduction by
hydrazine at ca. 95 8C for 1 h. Graphene paper was prepared by
filtration of a measured amount of the resulting colloid through an
Anodisc membrane filter (47 mm in diameter, 0.2 mm pore size,
Whatman), followed by air drying and peeling from the filter. Unless
Figure 4. Fluorescence microscopy image of calcein-stained L-929 cells specifically stated, graphene paper with a thickness of around 6 mm was
growing on graphene paper. used for all measurements reported in this work. These samples of
graphene paper were annealed at different temperatures in air
(<220 8C) or argon (>220 8C) for 1 h before being cooled to room
temperature for various measurements. For comparison, GO paper was
are significantly reduced when treated at 220 8C (Fig. 2B and C) also prepared, using a similar filtration method, as reported in Ref. [4].
as a sequence of structural destruction caused by thermal Structural and Properties Characterization: The thermal properties
decomposition (Fig. S1 of the Supporting Information). of the graphene papers were characterized by TGA (Q500, TA
Carbon materials have proven to be promising for Instruments). All measurements were conducted under air or nitrogen
gas at a flow rate of 40 mL min1 over a temperature range of 30–800 8C
biomedical applications such as tissue engineering and with a ramp rate of 5 8C min1. The XRD patterns of graphene paper
implants, in part because of their inherent biocompatibil- samples annealed at different temperatures were recorded on an
ity.[21–26] To our knowledge, there have been no reports Australia GBC Scientific X-ray diffractometer (40 kV, 20 mA, Cu Ka
regarding the biocompatibility of chemically prepared gra- radiation, l ¼ 1.5418 Å) at room temperature. Static uniaxial in-plane
tensile tests were conducted with a dynamic mechanical analyzer
phene-based materials. Graphene paper offers an ideal
(DMA Q800, TA Instruments). The samples were cut with a razor into
platform for cell culture experiments owing to the ease of rectangular strips of approximately 3  15 mm2 for mechanical testing
handling. Initial biocompatibility assessment of the graphene and were gripped using a film tension clamp with a clamp compliance of
papers was addressed by culture of the mouse fibroblast cell about 0.2 mm N1. All tensile tests were conducted in controlled strain
line (L-929), which is commonly used to assess cytotoxicity of rate mode with a preload of 0.01 N and a strain ramp rate of
0.05% min1. Conductivity measurements were carried out on a Jandel
potential substrates for cell growth, and has been used RM3 Conductivity Meter using a four-point probe head. SEM images
previously in biocompatibility testing of carbon nanotubes.[25] were obtained using a Hitachi S-900 field-emission scanning electron
L-929 cells were found to adhere to and proliferate on the microscope operated at an accelerating voltage of 4 kV.
graphene papers, such that by 48 h of culture time a Biocompatibility Test: Graphene paper that was thermally annealed
subconfluent layer of metabolically active cells could be at 100 8C was screened for biocompatibility by monitoring the growth of
visualized (Fig. 4). The doubling time for the cells was the same L-929 (mouse fibroblast) cells. The graphene paper samples were placed
into wells of a 96-well polystyrene cell culture plate and soaked overnight
on graphene papers as on commercial polystyrene tissue in two changes of culture media, then rinsed with water to remove soluble
culture plastic (data not shown), indicating normal prolifera- impurities. The samples were sterilized by rinsing with 70% ethanol,
tion rates on these materials. Thus, graphene paper provides a followed by air-drying and placing under UV light for 20 min. Samples
good substrate for the adhesion and proliferation of L-929 were seeded with 5  103 L-929 mouse fibroblast cells per well, and
cultured in DMEM/F12 media supplemented with 5% FBS for 48 h.
cells, suggesting that chemically prepared graphene may be a
Finally the cells were stained with Calcein AM, which is cleaved to yield
biocompatible material. a green fluorescent product by metabolically active cells. Images were
In summary, we have demonstrated that highly ordered obtained using a Leica DMIL inverted fluorescence microscope
graphene paper can be prepared by directional flow-induced equipped with a Leica DC500 camera.
assembly of graphene sheets that are well dispersed in solution.
Received: March 18, 2008
Moderate thermal annealing can enhance its mechanical
Revised: May 14, 2008
stiffness and strength as well as electrical conductivity. We Published online: July 23, 2008
have also presented the results of cell culture experiments,
which indicate that graphene paper may be biocompatible and
therefore suitable for biomedical applications. The combina-
tion of the exceptional mechanical strength, thermal stability,
high electrical conductivity, and biocompatibility makes
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