FULL PAPER

DOI: 10.1002/chem.201102646

Mixed Colloidal Suspensions of Reduced Graphene Oxide and Layered

Metal Oxide Nanosheets: Useful Precursors for the Porous Nanocomposites
and Hybrid Films of Graphene/Metal Oxide

Yu Ri Lee, In Young Kim, Tae Woo Kim, Jang Mee Lee, and Seong-Ju Hwang*[a]

Abstract: Homogeneously mixed col-
loidal suspensions of reduced graphene
oxide, or RGO, and layered manganate
nanosheets have been synthesized by a
simple addition of the exfoliated col-
loid of RGO into that of layered
MnO2. The obtained mixed colloidal
suspensions with the RGO/MnO2 ratio
of  0.3 show good colloidal stability
without any phase separation and a
negatively charged state with a zeta (z)
potential of 30 to 40 mV. The floc-
culation of these mixed colloidal sus-
pensions with lithium cations yields
porous nanocomposites of Li/RGO-lay-
ered MnO2 with high electrochemical
activity and a markedly expanded sur-
face area of around 70–100 m2 g1. Rel-
ative to the Li/RGO and Li/layered
MnO2 nanocomposites (  116 and
 167 F g1), the obtained Li/RGO-lay-
ered MnO2 nanocomposites deliver a
larger capacitance of approximately
210 F g1 with good cyclability of
around 95–97 % up to the 1000th cycle,
thus indicating the positive effect of hy-
bridization on the electrode perform-
Keywords: composites · electrodes ·
hybrid materials · nanomaterials ·
self-assembly
ances of RGO and lithium manganate.
Also, an electrophoretic deposition of
the mixed colloidal suspensions makes
it possible to easily fabricate uniform
hybrid films composed of graphene
and manganese oxide. The obtained
films show a distinct electrochemical
activity and a homogeneous distribu-
tion of RGO and MnO2. The present
experimental findings clearly demon-
strate that the utilization of the mixed
colloidal suspensions as precursors pro-
vides a facile and universal methodolo-
gy to synthesize various types of gra-
phene/metal oxide hybrid materials.

Introduction pore structure and strongly coupled electronic structure.[10–13]

The unique physicochemical properties and many valuable
functionalities of nanostructured materials have inspired a
great deal of research on the synthesis and applications of
various low-dimensional nanostructures such as 0D quantum
dots and 1D nanowires/nanotubes.[1–3] Currently, research ac-
tivity on the nanostructured materials has extended to 2D
nanostructures such as nanosheets and nanoplates.[3–5] One
of the most useful chemical methods to synthesize 2D nano-
sheets is an exfoliation of layered inorganic solids into indi-
vidual layers.[6–8] The exfoliated 2D nanosheets are obtained
in the form of a stable colloidal suspension in aqueous
media or organic solvent.[7, 8] A distinct surface charge of ex-
foliated colloidal nanosheets renders them powerful building
blocks for many novel hybrid materials such as intercalative
nanohybrids, layer-by-layer-ordered multilayer films, hollow
spheres, and so on.[7–10] The reassembling of anionic transi-
tion-metal oxide nanosheets with cationic guest species
yields highly porous pillared metal oxides with a tailored
[a] Y. R. Lee, I. Y. Kim, T. W. Kim, J. M. Lee, Prof. S.-J. Hwang
Center for Intelligent Nano-Bio Materials (CINBM)
Department of Chemistry and Nano Sciences
Ewha Womans University, Seoul 120-750 (Korea)
Fax: (+ 82) 2-3277-3419
E-mail: hwangsju@ewha.ac.kr
Supporting information for this article is available on the WWW
under http://dx.doi.org/10.1002/chem.201102646.
If we take into account the remarkably expanded surface
area and redox capability of component transition-metal
ions, the reassembled nanohybrids of transition-metal oxide
nanosheets are supposed to show promising electrode per-
formance for supercapacitors and lithium-ion batteries.[13]
Since the component transition-metal oxides possess rela-
tively poor electrical conductivity, the electrode perfor-
mance of these nanosheet-assembled materials can be fur-
ther improved by the hybridization with conductive carbon
species. Given the common 2D morphology of graphene
and transition-metal oxide nanosheets, the combination of
these two materials is expected to yield strongly coupled
nanohybrid materials with optimized functionalities. Of
prime importance is that, like the exfoliated nanosheets of
layered metal oxide, graphene can be prepared in the form
of an aqueous colloidal suspension of reduced graphene
oxide, or RGO, nanosheets.[14] Thus these two colloidal
nanosheets are supposed to easily form homogeneously
mixed suspensions in aqueous media. Since the exfoliated
nanosheets of RGO and transition-metal oxide commonly
possess negative surface charge,[15] an electrostatically de-
rived self-assembly of this mixed suspension with cationic
species can produce the intimately coupled nanocomposites
of RGO/transition-metal oxide. The hybrid films of RGO
and transition-metal oxide can also be fabricated by an elec-
trophoretic deposition of the mixed colloidal suspensions.
Thus the preparation of the mixed suspension of RGO and

Chem. Eur. J. 2012, 18, 2263 – 2271  2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim 2263
layered metal oxide nanosheets can provide a facile and uni-
versal methodology to synthesize various types of graphene/
metal oxide hybrid materials. To date, however, there has
been no report on the preparation of a mixed colloidal sus-
pension that contains RGO and layered transition-metal
oxide nanosheets, and its application for the synthesis of the
porous nanocomposites and hybrid films of RGO/metal
oxide.
In this study, the mixed colloidal suspensions of RGO and
layered MnO2 nanosheets were synthesized by the addition
of the exfoliated colloid of RGO into that of layered manga-
nate. The lithiated nanocomposites of Li/RGO-layered
MnO2 were obtained by the flocculation of the obtained
mixed colloidal suspensions with Li cations, whereas the ho-
mogeneous hybrid films of RGO and layered MnO2 were
fabricated by an electrophoretic deposition of the mixed col-
loidal suspensions. The crystal structure, crystal morphology,
and chemical-bonding nature of the obtained nanocompo-
sites and hybrid films were investigated with several diffrac-
tion, microscopic, and spectroscopic techniques. The electro-
chemical activity of the nanocomposites and the hybrid
films was examined not only to probe the applicability of
these materials as electrodes for supercapacitors but also to
elucidate the effect of hybridization on the electrode per-
formances of RGO and layered manganese oxide.
Results and Discussion
Mixed colloidal suspensions of RGO and layered MnO2
nanosheets: The colloidal suspension of RGO nanosheets
was mixed with that of exfoliated layered manganese oxide,
thereby leading to the formation of homogeneously mixed
suspensions of RGO and layered MnO2 nanosheets. The ob-
tained mixed colloidal suspensions showed good dispersion
ability and high colloidal stability without any phase separa-
tion for several weeks. As illustrated in the top panel of
Figure 1, three kinds of mixed colloidal suspensions were
obtained with the mixing ratios of RGO/MnO2 = 0.1:1, 0.2:1,
and 0.3:1 in mass. As the content of RGO increased, the
color of the mixed colloidal suspension became darker. At
higher RGO/MnO2 ratios of  0.4, the mixed colloidal sus-
pension was less stable, thus leading to the aggregation of
colloidal particles within a couple of hours.
The bottom left panel of Figure 1 represents the UV/Vis
absorption spectra of the mixed colloidal suspensions of
RGO and layered MnO2 nanosheets compared with the ref-
erence spectrum of the pure colloidal suspension of RGO or
layered MnO2 nanosheets. A broad absorption peak that
corresponds to the d–d transition of Mn ions in the MnO6
octahedra was observed at approximately 380 nm for the
pure colloidal suspension of layered MnO2 nanosheets.[16]
Conversely, the colloidal suspension of RGO displayed a
strong peak at around 276 nm and a significant absorption
at longer wavelength region. As shown in the bottom left
panel of Figure 1, the mixed colloidal suspensions displayed
an intense and broad peak at around 380 nm that corre-
2264 www.chemeurj.org  2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Figure 1. Photo images (top) and UV/Vis absorption spectra (bottom
left) of a) the pure colloidal suspension of the layered MnO2 nanosheets
and the mixed colloidal suspensions with RGO/MnO2 ratios of b) 0.1,
c) 0.2, d) 0.3, and e) the pure colloidal suspension of the RGO nano-
sheets. Bottom right: HRTEM image of the colloidal nanosheets from
the mixed colloidal suspension with an RGO/MnO2 ratio of 0.3.
sponds to the layered MnO2 nanosheets but no well-separat-
ed peak at around 276 nm that would be related to the
RGO nanosheets. The observed spectral features are attrib-
uted to the higher content of layered MnO2 than RGO in
the present colloidal suspensions, which leads to the con-
cealment of the RGO-related peak by the stronger MnO2-
related peak. With the increase in the RGO/MnO2 ratio, the
absorption peak at around 380 nm became depressed, there-
by indicating a decrease in the concentration of layered
MnO2 nanosheets. In addition, an increase of the RGO/
MnO2 ratio gave rise not only to an increase in the ratio of
absorption intensity at around 276/380 nm but also to the
enhancement of background absorption at > 550 nm, there-
by confirming the increase in RGO concentration.
The crystal shapes of colloidal particles in the mixed sus-
pension were examined with high-resolution (HR) TEM
analysis (see the bottom right panel of Figure 1). Two differ-
ent types of sheet-like crystals can be observed from the
HRTEM image of the mixed colloidal suspension. The
larger irregular-shaped crystallites with very weak contrast
correspond to the RGO nanosheets, whereas the smaller
rectangular-shaped crystallites with stronger contrast are at-
tributed to layered MnO2 nanosheets. The particle size of
the layered MnO2 nanosheets is around 0.2–0.4 mm, whereas
the RGO nanosheets possess a much larger particle size of
several micrometers. Due to the very thin thickness and
high flexibility of the RGO nanosheet, this sheet-shaped
particle shows many folded areas with stronger contrast.
The coexistence of two kinds of nanosheets provides strong
evidence for the homogeneous mixing of these species in
the mixed colloidal suspension. In addition, the surface
charges of the obtained colloidal suspensions were examined
with zeta (z) potential measurements. All of the present sus-
Chem. Eur. J. 2012, 18, 2263 – 2271
Mixed Colloidal Suspensions
pensions commonly display an average z potential of 30 to
40 mV, thereby indicating the negatively charged state of
exfoliated RGO and layered MnO2 nanosheets. The nega-
tively charged state of these nanosheets allows us to synthe-
size homogeneously coupled nanocomposites of RGO-lay-
ered MnO2 by means of flocculation with lithium cations.
Powder XRD analysis of lithiated nanocomposites: Three
kinds of lithiated nanocomposites were synthesized by the
mixing of Li + cations and mixed colloidal suspensions with
a mass ratio of RGO/MnO2 = 0.1:1, 0.2:1, and 0.3:1 (the ob-
tained materials are denoted LGM1, LGM2, and LGM3, re-
spectively). After adding lithium ions, the flocculation of
colloidal particles occurred immediately, a result of an elec-
trostatic interaction between the negatively charged nano-
sheets and lithium cations. After the flocculation, the re-
maining supernatant solution became transparent, which
strongly suggested the complete precipitation of both RGO
and layered MnO2 nanosheets.
The powder X-ray diffraction (PXRD) patterns of the Li/
RGO-layered MnO2 nanocomposites are plotted in Figure 2,
FULL PAPER
based nanocomposite, the MnO2-free Li/RGO nanocompo-
site displays no distinct (00l) Bragg reflections, thus indicat-
ing the disordered stacking of RGO nanosheets.[17] A very
thin RGO nanosheet seems too flexible to form a rigid in-
tercalation structure with oppositely charged lithium cations.
On the basis of this finding, the negligible difference be-
tween the XRD patterns of the Li/RGO-layered MnO2
nanocomposites and the RGO-free Li/layered MnO2 nano-
composite can be regarded as evidence for the disordered
incorporation of flexible RGO nanosheets in the nanocom-
posite lattice. As can be seen from Figure 2, the in-plane
(100) and (110) reflections of the layered MnO2 structure
are still discernible in the XRD patterns of the present Li/
RGO-layered MnO2 nanocomposites, which clearly demon-
strates the maintenance of the hexagonal in-plane structure
of manganese oxide layers after the composite formation.
Micro-Raman and FTIR spectroscopy of LGM nanocompo-
sites: The presence of RGO nanosheets in the Li/RGO-lay-
ered MnO2 nanocomposites was examined with micro-
Raman and FTIR spectroscopy together with the chemical-
bonding nature of the incorporated RGO component. The
top panel of Figure 3 represents the micro-Raman spectra of
the Li/RGO-layered MnO2 nanocomposites compared with

Figure 2. Powder XRD patterns of a) pristine K0.45MnO2, b) the protonat-

ed manganese oxide, c) the Li/layered MnO2 nanocomposite, the Li/
RGO-layered MnO2 nanocomposites of d) LGM1, e) LGM2, and
f) LGM3, and g) the Li/RGO nanocomposite.

compared with those of the pristine K0.45MnO2, its protonat-

ed derivative, the Li/layered MnO2 nanocomposite, and the
Li/RGO nanocomposite. Like the pristine potassium manga-
nese oxide and its protonated derivative, all of the present
MnO2-based nanocomposites exhibit well-developed (00l)
reflections at the low 2q region, thus indicating the forma-
tion of a well-ordered intercalation structure. From the
least-squares fitting analysis, the basal spacings of all the Li/
RGO-layered MnO2 nanocomposites were determined to be
approximately 7.1 . The negligible dependence of basal
spacing on the content of RGO suggests that the crystal
framework of the present nanocomposite is mainly deter-
mined by the layer-by-layer ordering of MnO2 nanosheets
with lithium ions. This supposition is further supported by a
close similarity between the basal spacings of the Li/RGO- Figure 3. Micro-Raman (top) and FTIR spectra (bottom) of the Li/RGO-
layered MnO2 nanocomposites and that of the RGO-free layered MnO2 nanocomposites of a) LGM1, b) LGM2, c) LGM3,
Li/layered MnO2 nanocomposite. In contrast to the MnO2- d) RGO, and e) graphite oxide.

Chem. Eur. J. 2012, 18, 2263 – 2271  2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim www.chemeurj.org 2265

those of RGO and graphite oxide. All of the Li/RGO-lay-
ered MnO2 nanocomposites displayed two strong peaks at
around 1318 and around 1592 cm1, which are characteristic
of graphene. This finding provides strong evidence for the
incorporation of RGO nanosheets in these materials. The
lower-energy D band is attributed to the k-point phonons of
A1g symmetry, whereas the higher-energy G band originates
from zone-center phonons of E2g symmetry.[18, 19] Since the
D-mode phonon is optically active only in the presence of
disorder, the peak intensity can act as an indicator for the
disorder of carbon species.[20] The Li/RGO-layered MnO2
nanocomposites showed nearly the same intensity ratio of
the D/G peaks as RGO, thereby indicating the negligible in-
fluence of composite formation on the chemical-bonding
nature of RGO nanosheets.[17] As the ratio of RGO/MnO2
in the reactant increased, the intensities of both the D and
G peaks became stronger, which confirms the increase in
RGO content in the obtained nanocomposites. In the low-
wavenumber region, two distinct peaks appeared at around
480 and around 600 cm1, which correspond to the vibra-
tions of oxygen ions in the manganate lattice. The observed
spectral features are characteristic of birnessite-type layered
manganate lattice,[21] thereby confirming the maintenance of
a layered MnO2 lattice after hybridization with RGO nano-
sheets.
The FTIR spectra of the Li/RGO-layered MnO2 nano-
composites are illustrated in the bottom panel of Figure 3 in
comparison with those of graphite oxide and RGO. Whereas
the graphite oxide exhibited strong IR bands that corre-
spond to the carbonoxygen bonds in the wavenumber
region of 900–1800 cm1,[22, 23] these bands are much weaker
for the RGO, which confirms the reduction of oxygenated
functional groups. Like the RGO material, all the present
nanocomposites showed only weak intensity for these fea-
tures, thus verifying little change in the RGO component
upon formation of the composite.
Elemental analysis and thermogravimetric analysis (TGA)
of LGM nanocomposites: The chemical compositions of the
Li/RGO-layered MnO2 nanocomposites were probed using
inductive coupled plasma (ICP) spectrometry and TGA.
The Li/Mn ratio of the present nanocomposites was evaluat-
ed to be 0.4 for LGM1, 0.5 for LGM2, and 0.4 for LGM3.
Since both RGO and layered MnO2 nanosheets possess sim-
ilar layer charge, there is no clear dependence of Li/Mn
ratio on the amount of RGO nanosheets. However, a higher
Li content of the LGM2 material than the other nanocom-
posites strongly suggests that this material has a more ap-
propriate pore structure to accommodate more lithium ions.
The contents of water and RGO in the Li/RGO-layered
MnO2 nanocomposites were examined with TGA. As shown
in Figure 4, a significant mass loss of around 12.5–15.0 %
was discernible for all the nanocomposites in the tempera-
ture region of 25–200 8C, which is attributed to the evapora-
tion of surface-adsorbed and intercalated water molecules.[24]
In contrast to the Li/layered MnO2 nanocomposite, the Li/
RGO-layered MnO2 nanocomposites showed an additional
2266 www.chemeurj.org  2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
S.-J. Hwang et al.
Figure 4. TGA curves of the Li/RGO-layered MnO2 nanocomposites of
a) LGM1, b) LGM2, c) LGM3, and d) the Li/layered MnO2 nanocompo-
site.
mass loss at 200–360 8C, which is attributed to the removal
of oxygenated groups of RGO component. In the higher-
temperature region of > 400 8C, all the present Li/RGO-lay-
ered MnO2 nanocomposites displayed another mass de-
crease that corresponded to the evolution of oxygen from
the manganate lattice, thereby resulting in the reduction of
Mn4 + ion to Mn3 + ion and the formation of an Mn3O4
phase. From the TGA results, the mass percent of RGO
components in the nanocomposites was calculated to be 7 %
for LGM1, 9 % for LGM2, and 11 % for LGM3, respective-
ly. On the basis of the ICP and TGA results, the chemical
compositions of the present nanocomposites were deter-
mined to be Li0.4MnO2·0.78 H2O·0.3 C for LGM1,
Li0.5MnO2·0.93 H2O·0.35 C for LGM2, and
Li0.4MnO2·1.00 H2O·0.4 C for LGM3, respectively.
Field-emission scanning electron microscopy (FESEM) and
elemental mapping analyses of LGM nanocomposites: The
crystal morphology of the Li/RGO-layered MnO2 nanocom-
posites was examined with FESEM analysis (see Figure 5).
Except for the pristine potassium manganate, all the present
Li/RGO-layered MnO2 nanocomposites showed a porous
crystal morphology formed by the house-of-cards-type
stacking of layered MnO2 and/or RGO nanosheets. A simi-
lar crystal shape appeared not only for the RGO-free Li/lay-
ered MnO2 nanocomposite but also for the MnO2-free Li/
RGO one. This finding indicates that the porous structure of
the present nanocomposites can be created by the stacking
of layered MnO2 nanosheets and/or RGO nanosheets. This
is further supported by the negligible influence of RGO
content on the crystal morphology of the present Li/RGO-
layered MnO2 nanocomposites. The observation of a much
more porous structure for the reassembled nanocomposites
than for the pristine K0.45MnO2 highlights the usefulness of
the reassembling process of nanosheets in providing layered
metal oxide with considerable porosity. The elemental distri-
Chem. Eur. J. 2012, 18, 2263 – 2271
Mixed Colloidal Suspensions
Figure 5. FESEM images of the a) pristine layered K0.45MnO2, b) Li/lay-
ered MnO2 nanocomposite, c) Li/RGO nanocomposite, and the Li/RGO-
layered MnO2 nanocomposites of d) LGM1, e) LGM2, and f) LGM3.
bution of the Li/RGO-layered MnO2 nanocomposites was
probed with electron diffraction spectroscopy (EDS)/ele-
mental mapping analysis (see the Supporting Information).
Carbon and manganese elements were homogeneously dis-
tributed throughout the entire parts of the sample, thereby
confirming the formation of the homogeneous nanocompo-
site of layered manganate and RGO nanosheets.
N2 adsorption/desorption isotherm measurements of LGM
nanocomposites: The surface area and porosity of the Li/
RGO-layered MnO2 nanocomposites were examined with
N2 adsorption/desorption isotherm measurements. As plot-
ted in Figure 6, the present nanocomposites commonly
showed fairly efficient adsorption of nitrogen with distinct
hysteresis in the high-pressure region of p/p0 > 0.45, thereby
reflecting the formation of mesopores upon the reassem-
bling process. The observed isotherms and hysteresis behav-
iors of the Li/RGO-layered MnO2 nanocomposites can be
interpreted as Brunauer–Deming–Deming–Teller (BDDT)
type I and IV isotherm and H3-type hysteresis loop in the
IUPAC classification.[25] This indicates the presence of open
slit-shaped capillaries with very wide bodies and narrow
short necks. Almost identical isotherms could be detected
for the RGO-free Li/layered MnO2 nanocomposite. Con-
versely, there was no distinct hysteresis with only a weak N2
adsorption in the isotherm of the Li/RGO nanocomposite,
thus reflecting its nonporous nature. This observation seems
to contrast with the porous morphology of this material in
Chem. Eur. J. 2012, 18, 2263 – 2271  2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
FULL PAPER
Figure 6. N2 adsorption/desorption isotherms of the a) Li/layered MnO2
nanocomposite, b) Li/RGO nanocomposite, the Li/RGO-layered MnO2
nanocomposites of c) LGM1, d) LGM2, e) LGM3, and f) the pristine lay-
ered K0.45MnO2. The open and closed symbols represent the adsorption
and desorption data, respectively.
the FESEM image (Figure 5c). Such a discrepancy is attrib-
utable to the effect of heat treatment in the degassing step
for the N2 adsorption/desorption isotherm measurement.
The degassing treatment at 150 8C causes a significant mass
decrease of the Li/RGO material, thereby indicating its
weak thermal stability. Such a weight decrease indicates the
evaporation of interlayer guest species in this material,
which leads to the formation of a dense packing structure of
the RGO nanosheets with a strong p–p interaction between
hexagonal graphene units. As a consequence, a very poor
porosity could be observed for this material in N2 adsorp-
tion/desorption isotherm measurements. The distribution of
pore size in all the nanocomposites under investigation was
estimated with the Barrett–Joyner–Halenda (BJH) method
(see the Supporting Information). All the Li/RGO-layered
MnO2 nanocomposites as well as the Li/layered MnO2 nano-
composite commonly possessed mesopores with an average
diameter of approximately 5 nm. There was no marked de-
pendence of pore size on the content of RGO nanosheets.
Given the smaller basal spacings of the present nanocompo-
sites than the diameter of mesopores, the formation of mes-
opores in these materials is ascribed to the porous house-of-
www.chemeurj.org 2267

cards-type assembly of the RGO/layered MnO2 sheet-like
crystallites. This is supported by the FESEM results
(Figure 5). In contrast, both the pristine K0.45MnO2 and Li/
RGO nanocomposite did not exhibit any distinct peak in
the pore distribution curves, thereby confirming the nonpo-
rous nature of these materials. According to the fitting anal-
ysis based on the BET equation, the surface areas of the Li/
RGO-layered MnO2 nanocomposites were estimated to be
approximately 73 m2 g1 for LGM1, approximately 99 m2 g1
for LGM2, and approximately 80 m2 g1 for LGM3, respec-
tively, which are larger than those of the Li/RGO nanocom-
posite (  2 m2 g1) and the Li/layered MnO2 nanocomposite
(  70 m2 g1). This finding underscores an advantage of the
mixed use of RGO and layered MnO2 nanosheets in synthe-
sizing highly porous materials. The expanded surface areas
of the present nanocomposites render them suitable for su-
percapacitor application.
Mn K-edge X-ray absorption near edge structure (XANES)
analysis of LGM nanocomposites: The oxidation state and
local crystal structure of manganese ions in the present
MnO2-based nanocomposites were investigated with Mn K-
edge XANES spectroscopy. Figure 7 plots the Mn K-edge
Figure 7. Left: Mn K-edge XANES spectra for the Li/RGO-layered
MnO2 nanocomposites of a) LGM1 (solid lines), b) LGM2 (dashed
lines), and c) LGM3 (dotted-dashed lines); d) the Li/layered MnO2 nano-
composite (dotted lines); e) the pristine K0.45MnO2 (asterisks); f) exfoliat-
ed MnO2 nanosheets (circles); g) b-MnO2 (squares);
h) LiMn0.9Cr0.1O2 (triangles). Right: The expanded views of the pre-edge
region of 6537–6545 eV. The symbols in parenthesis denote the data in
the expanded spectra.
XANES spectra of the Li/RGO-layered MnO2 nanocompo-
sites and the RGO-free Li/layered MnO2 nanocomposite,
compared with those of several references. The edge posi-
tions of the Li/RGO-layered MnO2 and Li/layered MnO2
nanocomposites are midway between those of LiMn3 +
4+
0.9Cr0.1O2 and b-Mn O2, thus indicating the mixed valence
3+ 4+
state of Mn /Mn in these materials. There is no notable
shift in the edge position depending on the content of RGO
nanosheets. All of the present materials showed weak pre-
edge peaks P and/or P’ that correspond to the dipole-forbid-
2268 www.chemeurj.org  2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
S.-J. Hwang et al.
den 1s!3d transition,[26] as shown in the right panel of
Figure 7. The observed weak intensity of these peaks indi-
cates the stabilization of manganese ions in centrosymmetric
octahedral symmetry. The present nanocomposites common-
ly displayed higher intensity for the peak P’ than for the
peak P. But the peak P’ was less intense for the nanocompo-
sites than for the tetravalent b-MnO2 reference. This obser-
vation confirms the mixed oxidation state of Mn3 + /Mn4 + in
these materials, since the relative intensity of the peaks P’/P
is proportional to the average oxidation state of Mn ions.[26]
In main-edge region, all the present materials exhibited sev-
eral peaks A and B that correspond to the dipole-allowed
1s!4p transitions. The intensity of the shakedown peak A
reflects the concentration of Jahn–Teller active Mn3 +
ions.[26, 27] In contrast to the reference LiMn0.9Cr0.1O2, which
shows an intense peak A, all the reassembled nanocompo-
sites as well as the pristine K0.45MnO2 displayed only a negli-
gible intensity for this peak. This finding can be interpreted
as evidence for the low concentration of Jahn–Teller active
Mn3 + ions in these materials. The intensity and sharpness of
the peak B was proportional to the ratio of edge-sharing of
MnO6 octahedra over corner-sharing ones.[28] Like the pris-
tine potassium manganate and Li/layered MnO2 nanocom-
posite, all the Li/RGO-layered MnO2 nanocomposites
showed an intense and sharp peak B, thereby confirming the
maintenance of a layered MnO2 lattice composed of edge-
sharing MnO6 octahedra after the formation of nanocompo-
sites.[28]
Electrochemical measurements of LGM nanocomposites:
The electrochemical activity of the Li/RGO-layered MnO2
nanocomposites was tested by carrying out cyclic voltamme-
try (CV) measurements. The CV data of the Li/RGO-lay-
ered MnO2 nanocomposites collected with the aqueous solu-
tion of 1.0 m Na2SO4 and the scan rate of 20 mV s1 are plot-
ted in Figure 8. Regardless of the content of RGO nano-
sheets, all of the present nanocomposites exhibited pseudo-
capacitance-type CV data without distinct redox peaks. The
effect of scan rate was also examined for the present nano-
and
Figure 8. CV data of the Li/RGO-layered MnO2 nanocomposites of
LGM1 (solid lines), LGM2 (dashed lines), and LGM3 (dot-dashed lines),
and the Li/layered MnO2 nanocomposite (dotted lines) collected with the
electrolyte of 1.0 m Na2SO4 solution.
Chem. Eur. J. 2012, 18, 2263 – 2271
Mixed Colloidal Suspensions
composites (see the Supporting Information). All of the Li/
RGO-layered MnO2 nanocomposites showed rectangular-
shaped CV curves even at a high scan rate of 100 mV s1,
thus indicating the high stability of their pseudocapacitance
behavior. The specific capacitance of the Li/RGO-layered
MnO2 nanocomposites was determined by performing galva-
nostatic charge/discharge cycling tests. The potential curves
of the present Li/RGO-layered MnO2 nanocomposites are
plotted in Figure 9, compared with those of Li/layered
Figure 9. Galvanostatic charge/discharge curves of the first few cycles and
a few cycles around the 1000th cycle at a constant current density
0.5 mA cm2 of the Li/RGO-layered MnO2 nanocomposites of a) LGM1,
b) LGM2, c) LGM3, d) the Li/layered MnO2 nanocomposite, and e) the
Li/RGO nanocomposite. f) Variations of the capacitance retention as a
function of the number of cycles for LGM1 (circles), LGM2 (triangles),
LGM3 (squares), the Li/layered MnO2 nanocomposite (diamonds), and
the Li/RGO nanocomposite (inverse triangles).
MnO2 and Li/RGO nanocomposites. A linear variation of
potential with time could be observed for all the materials
under investigation, which is indicative of capacitive behav-
ior of these materials. All of the present RGO-containing
nanocomposite materials showed large initial capacitances
of around 193 F g1 for LGM1, around 209 F g1 for LGM2,
and around 196 F g1 for LGM3, respectively. The specific
capacitances of the Li/RGO-layered MnO2 nanocomposites
were much larger than those of Li/RGO nanocomposite
(116 F g1) and Li/layered MnO2 nanocomposite
(167 F g1), thereby underscoring the advantage of the
composite formation in improving the specific capacitances
of RGO and layered MnO2 nanosheets.
The incorporation of highly conductive RGO nanosheets
can enhance the electrical conductivity of reassembled
MnO2 nanosheets, which is beneficial to the electrode per-
formance of the Li/RGO-layered MnO2 nanocomposites.
Chem. Eur. J. 2012, 18, 2263 – 2271  2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
FULL PAPER
However, the MnO2-free Li/RGO nanocomposite with high
RGO content showed a smaller specific capacitance than
the RGO-free Li/layered MnO2 nanocomposite, thereby in-
dicating the poorer electrode performance of the RGO
nanosheet than the layered MnO2 nanosheet. Hence a great
amount of RGO nanosheets is expected to decrease the
overall specific capacitance of the Li/RGO-layered MnO2
nanocomposite. As a consequence of the interplay of these
two factors, the largest capacitance among the present nano-
composites was obtained for LGM2 nanocomposite with in-
termediate RGO content. The observed dependence of spe-
cific capacitance on the LGO content for the present nano-
composites correlates well with the results of N2 adsorption/
desorption isotherm measurements and elemental analysis,
in which the LGM2 nanocomposite showed a larger surface
area and a higher lithium content than the other nanocom-
posites. These results obviously demonstrate that the LGM2
material has more appropriate pore structure for accommo-
dating a larger amount of lithium ions and thus for deliver-
ing larger specific capacitance. As plotted in Figure 9f, all of
the present Li/RGO-layered MnO2 nanocomposites exhibit
good cyclability of approximately 95–97 % up to the 1000th
cycle, thereby highlighting the high electrochemical stability
of the present nanocomposites. This sharply contrasts with
the poor stability of the Li/RGO nanocomposite with 70 %
retention, which confirms the synergetic effect of hybridiza-
tion on electrode performance. The excellent cyclability of
the present nanocomposites was cross-confirmed by the CV
measurements over 1000 cycles (see the Supporting Infor-
mation).
Hybrid films of RGO-layered MnO2 nanosheets: Hybrid
films composed of RGO and layered MnO2 nanosheets
were fabricated by an electrophoretic deposition of the pre-
cursor mixed colloidal suspensions. As plotted in Figure 10a,
dark brown films with a uniform surface were deposited on
the indium-doped tin oxide, or ITO, substrate. According to
XRD analysis (see the Supporting Information), the deposit-
ed films displayed similar XRD patterns to the lithiated
nanocomposite of RGO-layered MnO2, thereby reflecting a
structural similarity between the deposited materials and re-
assembled nanocomposites. FESEM analysis revealed the
smooth surface of the electrodeposited films (see Fig-
ure 10b). The elemental mapping data for the hybrid film
loaded onto the copper grid are also presented in Fig-
ure 10c–e. A clear cutting edge of the hybrid film is discerni-
ble with the bottom of copper grid from the FESEM image
(Figure 10c). Carbon and manganese elements were homo-
geneously distributed over the entire hybrid film but absent
in the copper grid part, thereby confirming the codeposition
of the RGO and layered MnO2 nanosheets in this film. As
plotted in Figure 10f, the CV measurements clearly demon-
strate the pseudocapacitance behaviors of the RGO-layered
MnO2 hybrid films, as observed in the Li/RGO-layered
MnO2 nanocomposites. Among the present hybrid films, the
film deposited from the mixed colloidal suspension with an
RGO/MnO2 ratio of 0.2 shows the highest electrochemical
www.chemeurj.org 2269

Figure 10. a) Photo images and b) top-view FESEM image of the hybrid
film. c) FESEM image and d, e) EDS mapping data of the hybrid film
loaded onto the copper grid. f) CV curves of the hybrid films of RGO
and layered MnO2 nanosheets deposited from the mixed colloidal sus-
pensions with RGO/MnO2 ratios of 0.1 (dotted–dashed lines), 0.2 (solid
lines), and 0.3 (dashed lines).
activity among the present films. This trend is in good agree-
ment with the CV results of the Li/RGO-layered MnO2
nanocomposites, in which the largest specific capacitance
was obtained for the LGM2 material. The present results in-
dicate that the mixed suspension of RGO and layered
MnO2 nanosheets can be used as an effective precursor for
hybrid films of RGO and manganese oxide with high elec-
trochemical activity.
Conclusion
Stable and homogeneous mixed colloidal suspensions of ex-
foliated RGO and layered MnO2 nanosheets were synthe-
sized and applied as precursors for lithiated nanocomposites
and hybrid films of RGO-layered manganate. The floccula-
tion of these mixed colloidal suspensions with lithium cat-
ions provided a facile synthetic route to porous nanocompo-
sites of Li/RGO-layered MnO2 nanocomposites with prom-
ising electrode functionality. A much larger specific capaci-
tance of around 210 F g1 could be obtained for the Li/
RGO-layered MnO2 nanocomposites, compared with the Li/
RGO and Li/layered MnO2 nanocomposites, which show
smaller capacitances of around 116 and around 167 F g1, re-
2270 www.chemeurj.org  2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
S.-J. Hwang et al.
spectively. The present findings verify the benefits of RGO
incorporation in optimizing the electrode activity of porous
metal oxide nanocomposite. In addition, the electrophoretic
deposition of the mixed suspensions allowed us to easily fab-
ricate hybrid films of RGO-layered MnO2 with uniform sur-
face structure and electrochemical activity. Thus, we can
conclude that an application of the mixed colloidal suspen-
sions of RGO and layered transition-metal oxide as precur-
sors provides a facile and simple route to synthesize diverse
types of hybrid materials that consist of graphene and metal
oxide. Similarly, the homogeneous and stable suspensions of
RGO and layered titanate nanosheets could be prepared by
a simple mixing of the colloidal suspensions of these two
kinds of nanosheets (see the Supporting Information). The
obtained mixed colloidal suspensions could also be utilized
as an effective precursor for the nanocomposites of layered
titanate and RGO. This fact clearly demonstrates that the
present synthetic routes that use mixed colloidal suspension
are readily applicable for many other colloidal nanosheets
of negatively charged inorganic solids. Our current project is
the exploration of new efficient hybrid-type electrode mate-
rials for supercapacitors by using other mixed colloidal sus-
pensions of RGO and metal oxide 2D nanosheets such as
layered ruthenium oxide and layered cobalt oxide.
Experimental Section
Preparation: As a precursor, the aqueous colloidal suspension of RGO
nanosheets was obtained by a modified Hummers method.[14, 29] To
remove the residual species such as hydrazine from the suspension, the
as-prepared suspension of RGO was purified by dialysis. As another pre-
cursor, the colloidal suspension of exfoliated layered MnO2 nanosheets
was prepared by the reaction between protonated K0.45MnO2 and tetrabu-
tylammonium hydroxide (TBA·OH).[30] The homogeneous mixed suspen-
sions of RGO and layered manganese oxide could be synthesized by
adding the colloidal suspension of RGO into that of layered MnO2. The
lithiated nanocomposites of exfoliated layered manganate/RGO nano-
sheets were synthesized by adding the mixed colloidal suspension of
MnO2/RGO nanosheets into the aqueous solution of lithium ions. After
reaction for 24 h at room temperature, powdery precipitates were re-
stored from the reactant suspension by centrifugation, washed thoroughly
with distilled water, and then dried. The resulting supernatant solution
was transparent, which indicated that all of the RGO and layered MnO2
nanosheets were incorporated into the precipitate of nanocomposite. The
obtained colloidal suspension was also applied to the fabrication of
hybrid films of RGO-layered MnO2. Before the electrophoretic deposi-
tion, the aqueous colloidal suspension was diluted with acetonitrile to
minimize the electrolysis of water during electrophoretic deposition. The
films were prepared by electrophoretic deposition of the diluted colloidal
suspensions on the ITO substrate with an applied voltage of 25 V.
Characterization: The optical properties and surface charge of the mixed
colloidal suspensions of exfoliated RGO and layered MnO2 nanosheets
were examined using a UV/Vis spectrometer and z potential measure-
ments, respectively. The crystal structures of the Li/RGO-layered MnO2
nanocomposites and the hybrid films were examined by XRD. The crys-
tal morphology and elemental distribution of the nanocomposites and
the hybrid films were probed using FESEM and EDS/elemental mapping
analysis. ICP spectrometry and TGA were carried out to determine the
chemical compositions and thermal behaviors of the obtained nanocom-
posites. Micro-Raman spectroscopic analysis was carried out using a JY
LabRam HR spectrometer with an Ar laser of 514.5 nm as an excitation
source. The presence of oxygenated functional groups in the nanocompo-
Chem. Eur. J. 2012, 18, 2263 – 2271
Mixed Colloidal Suspensions
sites was probed with FTIR spectroscopy. The surface area and porous
structure of the nanocomposites were examined with N2 adsorption/de-
sorption measurements at 77 K. The materials were degassed at 150 8C
for 2 h under vacuum before the isotherm measurement. Mn K-edge X-
ray absorption spectroscopic, or XAS, analyses were carried out with the
extended X-ray absorption fine structure, or EXAFS, facility installed at
the beamline 7C at the Pohang Accelerator Laboratory in Korea. XAS
data were collected at room temperature in a transmission mode using
gas-ionization detectors. All the present spectra were calibrated by meas-
uring the spectrum of Mn metal foil. The data analysis for the experimen-
tal spectra was performed by the standard procedure reported previous-
ly.[31]
Electrochemical measurements: The electrode functionality of the Li/
RGO-layered MnO2 nanocomposites was investigated using CV and gal-
vanostatic charge/discharge cycling tests. The electrochemical experi-
ments were done in a conventional three-electrode cell, in which a plati-
num mesh was adopted as counterelectrode and a saturated calomel elec-
trode, or SCE, was used as reference electrode. The working electrodes
were fabricated by mixing the active material (nanocomposites), acety-
lene black, and polyvinylidenefluoride, or PVDF, in a mass ratio of
75:20:5. The homogeneous slurry was obtained by stirring the mixed in
N-methylpyrrolidone for 1 h. The obtained slurry was pressed onto a
stainless steel substrate, and the electrode was dried in vacuum oven at
80 8C for 30 min. An aqueous solution of Na2SO4 (1.0 m) was utilized as
electrolyte. CV experiments were performed from 0.2 to 0.8 V at a scan
rate of 20–100 mV s1 using a potentiostat/galvanostat (WonA Tech). The
electrochemical activity of the deposited hybrid films was also monitored
by measuring CV data. CV data of hybrid films were collected in 0.2 m
Na2SO4 electrolyte from 0 to 1 V at a scan rate of 5 mV s1. The galvano-
static charge/discharge cycle was measured at a constant current density
of 0.5 mA cm2.
Acknowledgements
This work was supported by the National Research Foundation of Korea
Grant funded by the Korean Government (MEST) (NRF-2010-
C1AAA001-2010-0029065) and by the Core Technology of Materials Re-
search and Development Program of the Korea Ministry of Intelligence
and Economy (grant No. 10041232. The experiments at PAL were sup-
ported in part by MOST and POSTECH.
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Received: August 25, 2011
Published online: January 17, 2012
www.chemeurj.org 2271