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2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim 1
www.MaterialsViews.com
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Seung Yol Jeong, Sung Hun Kim, Joong Tark Han, Hee Jin Jeong, Soo Yeon Jeong,
and Geon-Woong Lee*
1. Introduction
Graphene has received much interest due to its superior
mechanical and electrical properties, including a high Young’s
modulus, high specific surface area, high electrical conduc-
tivity, and high carrier mobility.
[1–4]
Single-layer graphene
is a promising candidate for the production of electronic
devices, composites, and energy storage applications. Sev-
eral methods for producing single-layer graphene, including
mechanical cleavage, epitaxial growth, chemical vapor deposi-
tion (CVD), and chemically modified graphene (CMG), have
been described.
[5–8]
The CVD and CMG methods provide the
most practical approaches for adaptation
to large-scale manufacturing processes.
Here, we focused on the use of CMG for
solution-based electronics printing and the
mass production of high concentrated and
conductive single-layer graphene. The pro-
duction of CMG involves several essential
steps for the chemical exfoliation and sub-
sequent reduction of graphite oxide.
[9]
Col-
loidal suspensions of high-quality CMG,
which contain few oxygen functional
groups and defects, have been unobtain-
able due to the hydrophobic nature of
graphene. The synthesis of graphite
oxide was described by Brodie in 1859 as
a starting material for graphene.
[10]
The
synthetic methods typically used today are
those of Brodie, Saudenmaier, Hummers,
and Offman and involve extensive oxida-
tion by a strong acid to increase the inter-
layer distance in the graphite. Hummers’
method is the most common, and is the
fastest and most effective way to form an
aqueous dispersion with a large interlayer
distance typical of highly oxidized graphite
oxide.
[11]
Compared to the Hummers method, Brodie’s method
yields lower contamination and higher quality graphite oxide,
although the interlayer distance is small.
[12,13]
To improve the
exfoliation of graphite oxide prepared by Brodie’s method and
the dispersion GO, the pH should be controlled by addition of
NaOH or KOH. We used a modified Brodie method accordingly
to produce high-quality RGO. However, reduction of GO to
RGO tends to result in agglomeration in aqueous solutions due
to hydrophobic interactions among the RGO sheets.
[14]
A stable
dispersion of RGO is particularly important for preserving the
unique properties of the nanostructures. Surfactants, such as
polymers, have been introduced to reduce agglomeration;
[15]
however, the presence of polymers in RGO can alter the charac-
teristics of RGO that are most desirable for applications. Using
a modified Hummers method, Li et al. prepared an aqueous
dispersion of RGO without a polymeric surfactant by control-
ling the pH using ammonium ions and dialysis.
[16]
Park et al.
reported the preparation of a colloidal suspension containing
hydrazine-reduced potassium-modified RGO by addition of
aqueous KOH. These studies suggested that the introduction
Highly Concentrated and Conductive Reduced Graphene
Oxide Nanosheets by Monovalent Cation– π Interaction:
Toward Printed Electronics
A novel route to preparing highly concentrated and conductive reduced
graphene oxide (RGO) in various solvents by monovalent cation– π interac-
tion. Previously, the hydrophobic properties of high-quality RGO containing
few defects and oxygen moieties have precluded the formation of stable
dispersion in various solvents. Cation– π interaction between monovalent
cations, such as Na
+
or K
+
, and six-membered sp
2
carbons on graphene
were achieved by simple aging process of graphene oxide (GO) nanosheets
dispersed in alkali solvent. The noncovalent binding forces introduced by the
cation– π interactions were evident from the chemical shift of the sp
2
peak in
the solid
13
C NMR spectra. Raman spectra and the I- V characteristics dem-
onstrated the interactions in terms of the presence of n-type doping effect
due to the adsorption of cations with high electron mobility (39 cm
2
/Vs). The
RGO film prepared without a post-annealing process displayed superior elec-
trical conductivity of 97,500 S/m at a thickness of 1.7 μm. Moreover, mass
production of GO paste with a concentration as high as 20 g/L was achieved
by accelerating the cation– π interactions with densification process. This
strategy can facilitate the development of large scalable production methods
for preparing printed electronics made from high-quality RGO nanosheets.
DOI: 10.1002/adfm.201200242
Dr. S. Y. Jeong, S. H. Kim, Dr. J. T. Han, Dr. H. J. Jeong,
S. Y. Jeong, Dr. G.-W. Lee
Graphene Hybrid World Class Laboratory
Nano Carbon Materials Research Group
Korea Electrotechnology Research Institute (KERI)
Changwon, 641-120, Korea
E-mail: gwleephd@keri.re.kr
Adv. Funct. Mater. 2012,
DOI: 10.1002/adfm.201200242