ll

Article
Highly Ordered and Dense Thermally
Conductive Graphitic Films from a Graphene
Oxide/Reduced Graphene Oxide Mixture
Abozar Akbari, Benjamin V.
Cunning, Shalik R. Joshi, ...,
Pavel Bakharev, Gun-Ho Kim,
Rodney S. Ruoff

ben.cunning@gmail.com (B.V.C.)
ruofflab@gmail.com, rsruoff@ibs.re.kr
(R.S.R.)

HIGHLIGHTS
G-O films are prepared from
nematic-phase precursors using
the doctor blade method

Films are graphitized at 3,000 C,

pressed, and heated again at
3,000 C

Incorporating chemically reduced

G-O improves film density and
crystallinity

Mechanical press and second heat

treatment further improve density
and crystallinity

A new approach to make graphitic thin films from graphene oxide (G-O) is
presented. By incorporating small-diameter, reduced G-O platelets with G-O,
graphitized films show improved density and crystalline order when compared
with pure G-O. Mechanical pressing of the graphitized films increased density but
decreased crystallinity. A subsequent high-temperature heat treatment improved
atomic order beyond that seen before mechanical pressing. In-plane thermal
conductivity is on par with highly oriented pyrolytic graphite and exceeds
commercially available graphite-based thermal interface materials.

Akbari et al., Matter 2, 1198–1206

May 6, 2020 ª 2020 Elsevier Inc.
https://doi.org/10.1016/j.matt.2020.02.014
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Article
Highly Ordered and Dense Thermally
Conductive Graphitic Films from a Graphene
Oxide/Reduced Graphene Oxide Mixture
Abozar Akbari,1,2 Benjamin V. Cunning,1,* Shalik R. Joshi,3 Chunhui Wang,1
Dulce C. Camacho-Mojica,1 Shahana Chatterjee,1 Vijayakumar Modepalli,1 Collin Cahoon,1
Christopher W. Bielawski,1,4,5 Pavel Bakharev,1 Gun-Ho Kim,3 and Rodney S. Ruoff1,4,5,6,7,*

SUMMARY Progress and Potential

We report a new approach to making highly dense, oriented, and Highly oriented graphitic films are
crystalline graphite films from heat-treated and pressed graphene used as thermal interface
oxide (G-O). By introducing small-diameter reduced graphene oxide materials in portable electronics.
(rG-O) flakes into the graphene oxide starting material, we found Graphitic films derived from
that after heat treatment at 3,000 C, the sample density and atomic graphene oxide (G-O) could
order substantially improved over a film composed, at the outset, provide advantages, but
only of pure G-O flakes. A subsequent mechanical press increased graphitization of these films
the density but reduced the atomic order. A second 3,000 C heat results in significant expansion
treatment restored the graphitic structure with graphitization met- due to heat-induced
rics exceeding even those of the first heat treatment. The optimized decomposition of functional
graphitic film with an original concentration of 15 wt % reduced G-O groups on G-O. We report
in G-O gave well-oriented graphitic films with a density of 2.1 g methodology that significantly
cm 3, cross-plane thermal conductivity of 5.65 W m 1 K 1, and in- improves the quality of graphitic
plane thermal conductivity of 2,025 G 25 W m 1 K 1. films derived from G-O.

By incorporating a small fraction

INTRODUCTION of ‘‘very small’’-diameter reduced
Space constraints in miniature devices do not allow for large heatsinks, thus necessi- G-O platelets prior to film casting,
tating thin, highly conductive, and flexible heat spreaders for managing the thermal we observed less expansion and
dissipation effectively. A single layer of suspended graphene has one of the highest higher densities after
reported thermal conductivities exceeding 5,000 W m 1 K 11,2 but is not practical to graphitization. Mechanical
use as a heatsink material. Current industrial processes for the production of flexible pressing of these G-O-derived
heat spreaders rely on flexible pyrolytic graphite or graphitized polyimide having in- graphitic films can increase
plane thermal conductivity of ca. 1,950 W m 1 K 1 for the best samples.3 density but introduced defects. A
subsequent heat treatment
Graphite oxide is a form of graphite in which the layers of graphite are highly improved the crystallinity beyond
oxidized.4 The oxygen-containing functional groups on the basal plane and edges that prior to mechanical pressing.
allow stable and high-concentration dispersions of graphene oxide (G-O) in water Combining both approaches
and many other polar solvents.5–7 This liquid dispersibility allows for thin films yielded a dense, high-quality
(‘‘G-O paper’’) to be made by various techniques including vacuum filtration,8,9 spray graphitic film. The addition of
deposition,10,11 rod coating,12 the Langmuir-Blodgett method,13 electrochemical reduced G-O could be used in
deposition,14 and shear alignment.7 The oxidation of graphite disrupts the extended other heat-treated G-O materials
network of sp2 hybridized carbon and results in very poor thermal and electrical con- where increased density is
ductivities.15 Reduction of G-O can remove these functional groups, but high tem- desirable, e,g., G-O-derived
peratures are necessary to restore the graphitic sp2 structure.8 carbon fibers.

When stacked/overlapped G-O (including G-O paper) is thermally reduced, intersti-

tial water, as well as oxygen-containing functional groups in the G-O material itself,

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Figure 1. Schematic of the Fabrication Process

are released in gaseous form, resulting in significant expansion of the film due to
the voids created in the film.16 This can be desirable for some applications, such
as electrochemical energy storage, but not for thermal management.17 The density
of graphitic films can be increased by heating under pressure18 or the application of
pressure after heating,11,19,20 but reported densities of films made in this way
are limited to about 2.0 g cm 3, some 10% lower than the single-crystal density
of graphite (2.266 g cm 3). The reported thermal conductivities of the
pressed graphitic films made from G-O precursors vary widely, from below
1,000 W m 1 K 1 to 1,940 W m 1 K 1 (an extensive literature survey of the properties
of graphitic films derived from G-O is presented in Table S5). Here, we report a
method to fabricate highly dense, oriented, and thermally conductive graphitic films
from G-O by high-temperature treatment of a shear-aligned nematic mixture of G-O
flakes and ultrasmall-diameter reduced G-O flakes. Graphitizable precursors
including polymers21,22 and G-O23 have been used for densification of G-O-derived
films and fibers but our addition of small-diameter reduced G-O prevents the G-O
film from large expansion during the heat-treatment processes, increasing the den-
sity and improving the crystallographic texture of the resulting graphitic film.
1Center for Multidimensional Carbon Materials
(CMCM), Institute for Basic Science (IBS), Ulsan
RESULTS AND DISCUSSION 44919, Republic of Korea
2Nanoscale Science and Engineering Laboratory
The details of our approach for the preparation of graphitic films are depicted in Fig- (NSEL), Department of Mechanical and
ure 1 (experimental information can be found in Supplemental Information). Two Aerospace Engineering, Monash University
precursors were prepared for film fabrication: (1) a highly viscous nematic-phase Clayton, Clayton, VIC 3800, Australia
3School of Mechanical, Aerospace and Nuclear
gel of G-O and (2) a dispersion of small-diameter reduced G-O flakes (hereafter
Engineering, Ulsan National Institute of Science
referred to as rG-O) that was prepared by ultrasonication of commercial rG-O flake and Technology (UNIST), Ulsan 44919, Republic
material. The ultrasonicated rG-O was dispersed in the nematic-phase G-O gel by of Korea
4Schoolof Energy and Chemical Engineering,
mechanical grinding at concentrations from 0 to 25 wt %. Films were prepared using
Ulsan National Institute of Science and
shear alignment by a doctor blade7 to create films with G-O flakes aligned highly Technology (UNIST), Ulsan 44919, Republic of
parallel to the film.7,24,25 Because the oxygen present in G-O releases significant Korea
gas during heat treatment,8,26 the films were first ‘‘reduced’’ (i.e., deoxygenated) 5Department of Chemistry, Ulsan National
Institute of Science and Technology (UNIST),
by HI (aq) treatment prior to the first heating step; this reduces the gas-induced
Ulsan 44919, Republic of Korea
expansion during heat treatment. The films were then heated to 3,000 C in stages. 6Schoolof Materials Science and Engineering,
Ulsan National Institute of Science and
Because the density of high-temperature-treated G-O films is significantly lower Technology (UNIST), Ulsan 44919, Republic of
Korea
than that of graphite, compression of the films after heat treatment11,19,20 or during 7Lead Contact
heat treatment18 is an effective way of increasing their density, although to the best
*Correspondence:
of our knowledge all studies on G-O samples have used static pressing. Static press- ben.cunning@gmail.com (B.V.C.),
ing is not ideal for large-scale production, so we have used a rolling press that is ruofflab@gmail.com, rsruoff@ibs.re.kr (R.S.R.)
more suitable for incorporation as part of a production line. Because the mechanical https://doi.org/10.1016/j.matt.2020.02.014

Matter 2, 1198–1206, May 6, 2020 1199

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treatment of graphite is known to introduce defects in the lattice,27 we subjected the

samples to a second high-temperature treatment at 3,000 C in an attempt to restore
crystallographic order.

We use the following nomenclature for describing the samples in this article. In
rG-O_X-YC, X indicates the wt % of small-diameter rG-O flakes added to the
nematic-phase G-O during film preparation, and YC describes the temperature of
the heat treatment. ‘‘As prep.’’ and ‘‘HI’’ are used to indicate samples after doctor
blading and HI reduction, respectively. As an example, rG-O_20-2000C indicates
the sample containing 20 wt % of rG-O and that the final treatment stage was heating
at 2,000 C. Furthermore, we introduce YC_P (P for ‘‘pressed’’) to describe the sam-
ples after rolling-mill treatment (performed after the first 3,000 C heat treatment),
and YC_PH to describe samples after the second 3,000 C heat treatment. The evolu-
tion of G-O films in response to reduction and heat treatment has been extensively
reported,11,18–20 and the characterization of our films after reduction and the heat
treatments is documented extensively in Supplemental Information. In this paper
we focus on the effect of the incorporation of rG-O in the film and our mechanical
and subsequent heat treatment on the morphology and graphitization of the film.

To measure the effect of our treatment on the atomic order of our films, we used
X-ray diffraction (XRD) to measure the mean domain size in the (002) direction as a
metric for through-plane order (see Supplemental Information for details). Because
of the strong texture of our films and the Bragg-Brentano geometry of our X-ray
diffractometer, we could not probe the in-plane order of our films with XRD. Instead,
we used the full width at half-maximum (FWHM) of the Raman G band as a metric for
in-plane order.28 For XRD analysis, a higher value for the mean domain size indicates
higher order, while for Raman analysis, a smaller FWHM indicates higher in-plane or-
der. Mean domain sizes in the (002) direction and Raman G FWHM for samples
3000C, 3000C_P, and 3000C_PH are detailed in Figures 2A and 2B.

From measurements of both in-plane and through-plane graphitization metrics, we

observed a clear trend in the improvement of graphitization metrics by the addition
of rG-O for samples subjected to 3,000 C heat treatment but only up to the addition
of 15 wt %. Additions larger than 15 wt % resulted in metrics that were worse than the
samples without the rG-O addition. The Raman and XRD results also demonstrated
that the rolling press treatment (3000C_P) reduced both in-plane and cross-plane
atomic order. However, the second high-temperature heat treatment after rolling
improved the atomic order beyond that seen before rolling. We also measured all
of the 3000C_PH samples under tensile loading (Figure 2C) and found the tensile
strength also improved with increasing rG-O content, consistent with the trends
from XRD and Raman analysis.

To investigate the possible cause for the lower graphitization metrics in the samples
that contained rG-O additions higher that 15 wt %, we compared the As prep.
films using a polarized light microscope (Figure S4). We observed for rG-O_0 and
rG-O_15 that the G-O sheets are aligned parallel to the film surface; however, at
higher concentrations they are randomly oriented. Because graphite contains paral-
lel planes of carbon atoms, we postulate that having G-O sheets initially oriented
almost parallel to the surface rather than at random angles allows for improved
graphitization.

From the results presented in Figures 2A–2C, it was clear that 15 wt % (rG-O_15) is
the optimum addition of rG-O for high-quality graphitic films. To emphasize the

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Figure 2. Sample Graphitization Metrics

(A and B) (002) Mean domain size as measured by XRD (A) and Raman G band FWHM of samples heat treated to 3,000  C (B).
(C) Tensile strengths of 3000C_PH samples.
(D and E) Tensile strengths (D) and sheet resistances (E) of treatment with rG-O_0 and rG-O_15 at all stages of the treatments.

comparison between the optimum rG-O addition and pure G-O films, we focused
our comparisons on the rG-O_0 and rG-O_15 samples. In Figures 2D and 2E, we
compare the tensile strengths and sheet resistances of rG-O_0 and rG-O_15 at all
stages of film production. For rG-O_0 films, strong interlayer bonding in pure G-O
results in high tensile strengths, including in chemically reduced (HI) and low-heat-
treatment rG-O (1000C).

At a heat-treatment temperature at 2,000 C, graphitizable carbons undergo signif-

icant in-plane atomic reorganization forming planar (turbostatic) sp2 hybridized car-
bon and removing non-carbon atoms8,11,18 (see elemental analysis in Table S3). As a
result, the tensile strength of pure G-O films reduces significantly when heated to
2,000 C.11,23 In the case of rG-O_15 films, the incorporation of rG-O disrupted
the interlayer bonding and reduced film strength. As a result, we observed a signif-
icant decrease in the strengths for As prep., HI, and 1000C but the improvement in
sample quality due to the improved graphitization metrics results in higher tensile
strengths than pure G-O films for treatment temperatures higher than 2,000 C.
The addition of rG-O causes the sheet resistance to decrease for As prep. samples.
We observed lower sheet resistance values for the rG-O_15 samples for all treatment
conditions except at 3,000 C.

To examine the effect of our treatments and rG-O incorporation on film morphology,
we performed gas pycnometry density measurements and cross-section imaging
using both scanning and transmission electron microscopy (SEM and TEM). We
found that cross-section preparation by ‘‘cryogenic cracking’’ could not accurately

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Figure 3. Density and Cross-Sectional SEM Comparisons

(A) Density measurements of samples.
(B–E) Cross-sectional SEM images of rG-O_0-3000C (B), rG-O_15-3000C (C), rG-O_0-3000C_PH (D), and rG-O_15-3000C_PH (E). Note that the film
thickness of rG-O_0-3000C is significantly larger than that of rG-O_15-3000C, and the entire cross-section is not shown due to FIB depth limitation
z10 mm. Scale bars, 5 mm.

reproduce the true structure of the film interior (see Supplemental Information for
cross-sections prepared by cryogenic cracking and related discussion), and there-
fore prepared the cross-section samples by a focused ion beam (FIB).

The densities of As prep., 3000C, and 3000C_PH are shown in Figure 3A. For As
prep. films, we observed that the addition of rG-O slightly decreased the density
with increasing rG-O content. After the sample had been heat treated to 3,000 C
the sample density decreased significantly, and was much lower than the theoretical
density of graphite (z2.26 g cm 3). The density ranged from 0.3 g cm 3 for rG-O_0
to 1.5 g cm 3 for rG-O_15. The change of density with rG-O content matched
the trends seen in the graphitization metrics of Figure 2. This significant difference
in density is highlighted in the cross-sectional images of rG-O_0-3000C and
rG-O_15-3000C in Figures 3B and 3C.

Despite all As prep. films having almost the same thickness, we observed that the
cross-section of rG-O_0-3000C is clearly larger than that of rG-O_15-3000C (Figures
3B and 3C) due to its significant porosity. The incorporation of the rG-O clearly has a
positive effect on sample density prior to mechanical pressing, which we attribute to
two reasons. First, because the rG-O is already reduced it does not form gaseous
decomposition products when the film is heated; there is therefore less gas gener-
ated when compared with the pure G-O film. Second, the presence of rG-O causes a
reduction in the density of the As prep. samples (Figure 3A), and the lower density
may provide channels for gas escape from the film interior during heat treatment.

Compression of the films followed by a second heat treatment resulted in high-

density graphitic films, up to 2.1 g cm 3 for rG-O_15. The SEM cross-sections
of rG-O_0- and rG-O_15-3000C_PH are shown in Figures 3D and 3E (other

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Figure 4. Cross-Sectional TEM Comparisons

(A and B) Low-resolution cross-sectional TEM images of rG-O_0-3000C_PH (A) and rG-O_15-
3000C_PH (B). Electron contrast is observed due to voids in the film interior. The film surface is in
the horizontal direction of the image. Scale bars, 1 mm.
(C and D) High-resolution cross-sectional TEM images of rG-O_0-3000C_PH (C) and rG-O_15-
3000C_PH (D). Film surface is in the vertical direction of the image. Scale bars, 10 nm.

cross-sections can be seen in Figures S14–S20). Small voids were still visible in the
rG-O_0 sample but none were visible in the rG-O_15 sample. We also imaged these
cross-sections under TEM, detailed in Figure 4. Low-resolution imaging shows the
crystallographic texture of the (002) planes from contrast differences that arise
from regions of differing electron transparency (due to sample porosity).

For the rG-O_0 sample, the regions through the sample thickness that are more
electron transparent are not parallel with the film surface, whereas in the rG-O_15
sample they lie almost parallel to the film surface. High-resolution imaging of the
(002) lattice planes shows similar behavior. We observed numerous regions in the
rG-O_0-3000C_PH sample where (002) planes were found to intersect and then
diverge. In contrast, the rG-O_15-3000C_PH sample had (002) planes parallel in
most regions of the sample. We attribute this observation to the large difference
in thermally induced film expansion and void creation experienced by the samples
(Figures 3B and 3C). From our results, the rG-O_15 samples result in denser and
well-aligned graphitic films.

We attempted to characterize the thermal properties of the rG-O_0- and rG-O_15-

3000C_PH samples. Our samples were too thin to obtain a direct experimental mea-
surement of the in-plane thermal conductivity, so we used the optothermal Raman
technique in conjunction with finite-element analysis of the laser-induced heat
flow (using COMSOL Multiphysics software; see Supplemental Information for
detailed analysis) to determine the sample in-plane thermal conductivity.29 Because
the thermal conductivity for oriented graphite samples is anisotropic, we required a

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Figure 5. Thermal Characterization

(A) Graph of COMSOL-calculated in-plane thermal conductivity (k) as a function of the relevant
scaling factor (the ‘‘optothermal Raman factor,’’ see Supplemental Information for more details) for
two different laser spot sizes. The experimentally calculated optothermal Raman factor was 1.61 for
rG-O_15-3000C_PH. The extracted in-plane thermal conductivity is between 2,000 and 2,050 W
m 1 K 1 based on laser spot size uncertainty.
(B) False-color composite thermal image of thin strips of rG-O_0-3000C_PH and rG-O_15-
3000C_PH on a heat source (located to the left of the image) illustrating heat flow through the film.

cross-plane thermal conductivity value to accurately model the heat flow. Using the
3u method,30 we extracted a value of 5.65 W m 1 K 1 for rG-O_15-3000C_PH. In the
case of the rG-O_0 sample, the surface roughness was too high for us to be able to
accurately measure cross-plane thermal conductivity, and we analyzed only the ther-
mal conductivity of rG-O15-3000C_PH. Finite-element analysis gave an in-plane
thermal conductivity of 2025 G 25 W m 1 K 1 (Figure 5A; a range is presented
due to uncertainties in the laser spot size). We also compared the heat-flow charac-
teristics of these samples by bonding thin strips (5 3 40 mm) to a heating element
held at 95 C and imaging with an infrared camera (Figure 5B). The lateral heat trans-
fer is higher for the rG-O_15-3000C_PH film.

Here, we have described a new approach for creating highly oriented graphitic films
by combining G-O with small-diameter rG-O flakes. Films were cast using the doctor
blade method followed by heat treatment, roller pressing, and a second heat treat-
ment. By comparing different percentages of rG-O additions, we have determined
that the optimal amount of rG-O was 15 wt %. Reduction and heat treatment signif-
icantly expanded the film thickness due to the release of gas from the G-O, but the
addition of rG-O significantly reduced the film expansion during heating. Room-
temperature rolling of these films after high-temperature treatment increased the
film density but also increased atomic disorder. A final high-temperature treatment
was crucial in achieving highly oriented graphitic films with large in-plane and cross-
plane grain sizes. The thermal conductivity for our optimized sample exceeded
2000 W m 1 K 1. Furthermore, our experimental approach is adaptable to large-
scale preparation techniques: doctor blading, roll pressing, and heat treatment
are well-established industrial processing techniques.

EXPERIMENTAL PROCEDURES
For full details, please refer to Supplemental Information.

SUPPLEMENTAL INFORMATION
Supplemental Information can be found online at https://doi.org/10.1016/j.matt.
2020.02.014.

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ACKNOWLEDGMENTS
The authors would like to thank Dr. Fariborz Kargar for helpful discussions. This work
was supported by the Institute for Basic Science (IBS-R019-D1).
AUTHOR CONTRIBUTIONS
A.A., B.V.C., and R.S.R. conceived the project. A.A. and B.V.C. performed and
analyzed a majority of the experiments. B.V.C. and R.S.R. supervised the
project. Thermal characterization experiments were performed by S.R.J., B.V.C.,
and G.-H.K. S.C., V.M., C.C., C.W.B., and P.B. assisted in data acquisition and anal-
ysis. R.S.R. secured funding for the project. A.A., B.V.C., and R.S.R. wrote the manu-
script with input from all authors.
DECLARATION OF INTERESTS
The authors declare no competing interests.
Received: November 8, 2019
Revised: January 15, 2020
Accepted: February 18, 2020
Published: March 17, 2020
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