Electrochimica Acta 108 (2013) 465471

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Electrochimica Acta
j our nal homepage: www. el sevi er . com/ l ocat e/ el ect act a
A green hydrothermal approach for the preparation of
graphene/-MnO
2
3D network as anode for lithium ion battery
Yi Zhang
a,b
, Hao Liu
b,
, Zehua Zhu
a,
, Ka-wai Wong
b
, Rui Mi
b
,
Jun Mei
b
, Woon-ming Lau
b
a
School of Material Engineering, South West PetroleumUniversity, Chengdu, 610500, China
b
Chengdu Green Energy and Green Manufacturing Technology R&D Center, Chengdu Development Center of Science and Technology, China Academy of
Engineering Physics, Chengdu, 610207, China
a r t i c l e i n f o
Article history:
Received 15 April 2013
Received in revised form1 July 2013
Accepted 1 July 2013
Available online 8 July 2013
Keywords:
Graphene
Manganese dioxide nanocomposites
Lithium-ion battery
a b s t r a c t
Graphene/-MnO
2
nanocomposites (GMC) with high performance as anode material were synthesized
by a facile green procedure, in which we reduced graphene from graphene oxide and prepared the GMC
simultaneously through a conventional hydrothermal route. The samples are systematically investigated
by X-ray diffraction analysis, Raman spectroscopy, FT-IR spectroscopy, eld-emission scanning electron
microscopy, and transmission electron microscopy. The GMC presents a good reversible specic capac-
ity of 998 mAh g
1
at a current density of 60mA g
1
after 30 cycles and excellent rate capabilities of
590 mAh g
1
at a current density of 12A g
1
. The present results indicate that GMC nanocomposites have
enormous potential for application in lithium-ion batteries.
2013 Elsevier Ltd. All rights reserved.
1. Introduction
Lithium ion battery (LIB) is the most developed energy stor-
age device for various applications such as portable electronic
devices, electric vehicles, and sustainable energy generation sys-
tems because of their attractive high gravimetric and volumetric
energy densities compared with other energy storage techniques
[13]. However, rst introduced in the commercial market as the
anode material in LIBs, graphite has only a low specic capac-
ity (372mAh g
1
) and can hardly meet the increasing demand for
higher energy density [4]. A variety of nanostructured transition-
metal oxides have been widely investigated as anode materials for
LIBs due to their high theoretical capacity, environmental benig-
nity, non-formation of hazardous Li dendrites, and low cost [5,6].
Poizot et al. [7] rst introduced the concept of using nano-sized
transition-metal oxides (MO, where M is Co, Ni, Cu or Fe) as
anode electrode materials because due to their unique conversion
reactions, they were suggested to have even higher theoreti-
cal capacities (1000mAh g
1
) than graphite [8,9]. In particular,
nanostructured manganese oxides have been widely investigated
owing to their ideal electrochemical behavior, low cost, and envi-
ronmental compatibility [10,11]. Among them, manganese dioxide
(MnO
2
) is one of the most stable manganese oxides with excellent

Corresponding author. Tel.: +86 28 67076208; fax: +86 28 67076210.

Corresponding author. Tel.: +86 28 83034709.

E-mail addresses: mliuhao@gmail.com(H. Liu), zhu.zehua@163.com(Z. Zhu).
physical and chemical properties under ambient conditions [12,13]
and is expected to be one of the ideal candidates as anode electrode
material for LIB.
However, as other transition metal oxides, practical application
of MnO
2
in LIBs is limited due to its huge volume expan-
sion/contraction and particle polymerization during repeated
cycling processes, which lead to electrode breakdown, decrease of
inter-particle contact and poor cycling stability [14,15]. Carbon-
based composites have been exploited to solve these problems
[1618]. Lee et al. [16] and Yu et al. [17] found that the elec-
trochemical performance of manganese oxide can be improved
by carbon mixing, attributable to the much reduced dissolution
of Mn into the electrolyte from the resultant composite [18].
Recently, graphene, one of the most popular nano-materials, has
received considerable attention [19] because of its superior con-
ductivity, structure exibility, large surface area, and chemical
stability [20,21]. Graphene-based metal oxide composites (Co
3
O
4
[22], Mn
3
O
4
[23], Fe
3
O
4
[24]) have been reported as electrode
materials for LIBs, inwhichgraphene withits highconductivity and
electrochemical activity can form a 3D conductive network with
the metal oxide nanoparticles in metal oxide electrodes [25,26].
Specically, these transition-metal oxide/graphene nanocompos-
ites or hybrids are proved to be able to improve the rate capacity
and enhance the cycle life [27,28]. However, in general synthetic
strategies reported for the preparation of graphene/mental oxide
composites, such as chemical in situ deposition [2224], solgel
processes [27], and solid phase sintering process [28], graphene
has to be rstly reduced from graphene oxide in a separate
0013-4686/$ see front matter 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.electacta.2013.07.002
466 Y. Zhang et al. / Electrochimica Acta 108 (2013) 465471
process. Second, because of the low miscibility of graphene with
MnO
2
thesubsequent processes involvinggrapheneandMnO
2
usu-
ally suffer from uncontrolled agglomeration and growth of large
particles, which often lead to lowdispersibility and thus weakened
performance.
In this present work, we used the conventional hydrothermal
approach. However, we proved experimentally that instead of a
two-step process, we could reduce the graphene oxide and syn-
thesize the grapheneMnO
2
composite in a single step. Besides
process simplication, we proved that this procedure also provides
a simple and practical way to obtain a homogeneous network of
MnO
2
nanowires withcontrollablesize, shapeandcrystallinitycov-
ered with graphene. This nanostructured composite material was
shown to exhibit superior electrochemical performance with large
reversible capacity, high columbic efciency, excellent cyclic per-
formance and good rate capacity, showing a great potential and
promise as anode material in LIBs.
2. Experimental
2.1. Materials and characterization
Graphene oxide (GO) was prepared from natural graphite
powder (Qingdao Graphite Company) by the modied Hummers
method [29]. 2g natural graphite powder and 1.5g sodiumnitrate
(NaNO
3
) were mixed with 70ml surfuric acid (H
2
SO
4
, 98%) in ice
bath. Then 9g of potassium permanganate (KMnO
4
) was slowly
addedtothe solution, while keepthe mixture solutioninanice bath
for ve days. The solution was then diluted with 200ml of H
2
SO
4
(5%), and hydrogen peroxide (H
2
O
2
, 30%) was slowly added until
the solution turned green. The graphene oxide was recovered from
the mixture after wash procedure step by step until the solution
was closely in natural (pH6). The solution was then transferred
into freeze drying machine, the dry powder was GO.
The as-synthesized GO was prepared as a stable aqueous dis-
persion (1mg ml
1
, pH6) using ultrasonication. The -MnO
2
nanowires weresynthesizedbyhydrothermal methodwithKMnO
4
and hydrated manganese sulfate (MnSO
4
H
2
O) as precursors. In
a typical process, 0.158g KMnO
4
was added dropwise to 10ml
of 0.001M MnSO
4
H
2
O under magnetic stirring to form a pre-
cursor solution. After continuous stirring for a few minutes, the
solution was transferred into a Teon-lined stainless-steel auto-
clave, and the whole systemwas sealed and kept at 150

C for 15h.
Then the autoclave was cooled to room temperature. The product
was ltered, washed with distilled water, and then dried at 60

C
overnight in a vacuumoven.
To synthesize grapheneMnO
2
composites (GMC), a hydro-
thermal route was employed. 0.01g -MnO
2
was added to 20ml
GO solution (1mg ml
1
) and the mixture was sonicated for 2h to
make sure that the -MnO
2
was uniformly dispersed. Use of GO
instead of graphene here can ensure much better miscibility with
-MnO
2
than graphene. Then the hybrid solution was transferred
to a sealed 40ml Teon-lined autoclave again and heated to 90

C
for another 36h. The autoclave was then cooled to roomtempera-
ture. A hydrogel material of GMC was obtained from this process,
which was then taken out and washed with deionized water. The
prepared GMC was nally dried overnight at 60

C in vacuum.
The morphology and structure of the prepared samples were
characterized by eld-emission scanning electron microscopy (FE-
SEM, Hitachi S-5200), transmissionelectronmicroscopy(TEM, JEOL
JEM-100CX), high resolution transmission electron microscopy
(HRTEM, JEOL JEM2010), Fourier transformation infrared spec-
troscopy (FT-IR, Thermo IS10), Raman spectroscopy (micro-Raman
2000 systemRenishaw, Britain) thermal gravimetric analysis (TGA,
CTGA Q500 V20.10 Build 36, TG-DSC thermal analyzer measured
from room temperature to 600

C at a heating rate of 5

C/min in
air) and XRD systemequipped with Cu K

radiation (=1.5406

A).
2.2. Electrochemical measurements
To investigate the electrochemical behavior, the as-prepared
sample was assembled into CR2032 type coin cells in an Ar-
lled glove box with both moisture and oxygen below 1ppm.
The working electrodes were prepared by mixing 85wt.% active
GMC materials with 10wt.% conductive carbon black and 5wt.%
polyvinylidene uoride dissolved in N-methyl-pyrrolidone (NMP).
The slurry was then coated onto a copper foil and dried in a vac-
uumoven at 100

C overnight. The average loading amount of GMC

and -MnO
2
were 0.9556mg and 0.6526mg, respectively. And the
average electrode thickness of both materials was about 0.01mm.
Pure lithiumfoil was used as the counter electrode. The electrolyte
was 1M LiPF
6
in 1:1 (volumetric ratio) mixture of ethylene car-
bonate and dimethyl carbonate, and Celgard 2400 membrane was
used as the separator. The cells were galvanostatically discharged
and charged at different current densities in the voltage range
between 3.00V and 0.01V at room temperature on a battery test
system (BT2043, Arbin Instrument). Electrochemical impedance
spectroscopy (EIS) was measured by a electrochemical worksta-
tion in the frequency ranging from100kHz to 0.1Hz at open circuit
potential with an AC perturbation of 5mV.
3. Results and discussion
3.1. Material characterization and analysis
The microstructure and morphology of -MnO
2
and GMC mate-
rials were characterizedby SEMandTEM. It canbe seenfromFig. 1a
and c that the -MnO
2
possesses a nanowire structure with diam-
eter of 4050nm and length of 510m. As shown in Fig. 1b and
d, -MnO
2
remains the same in morphology but being wrapped by
a layer of graphite carbon, which would be proved to be graphene
reducedfromGO. Also, a 3Dnetworkwas observed, that couldwork
as a conductive material.
HRTEM analysis (Fig. 1c and d) shows a lattice spacing of
0.69nm, which agrees well with (110) interplanar distance of
-MnO
2
. The marked lattice fringes with a spacing of 0.28nm
are ascribed to the interplanar spacings (001) planes of -MnO
2
,
respectively. However, inFig. 1d, at theregionAwiththesamelevel,
we can clearly observe that image is focused on the carbon layer,
indicating that the -MnO
2
nanowires surface is covered with a
thin layer of graphene.
Fig. 2 shows the XRD patterns of -MnO
2
and GMC materials.
The as-synthesized nanowires can be identied as -MnO
2
since
all the reections in its XRD patterns can be readily indexed to a
pure tetragonal phase of -MnO
2
(ICDD-JCPDS No. 44-0141) with
lattice constants of a =0.9784nm and c =0.2863nm. For GMC, it
still shows the -MnO
2
crystal phase, while the weak and broad
diffraction peak around 2025

can be attributed to disorderedly

stacked graphene covering the MnO
2
nanowires.
Fig. 3 shows the TGA curves of the GMC as the temperature
increased from room temperature to 600

C. The GMC compos-

ite exhibited a slight weight loss of 2% at the beginning of the
test when the temperature increase from 25

C to 150

C, which
is attributed to the removal of adsorbed water. As the tempera-
ture went on increasing from150

C to 350

C, another 14% weight

loss was observed which corresponds to the loss of graphene. The
remaining material did not show any weight loss until the end of
the test, which is believed to be MnO
2
. Thus, the amount of MnO
2
in GMC material is estimated to be around 85wt.% excluding mois-
ture.
Y. Zhang et al. / Electrochimica Acta 108 (2013) 465471 467
Fig. 1. SEMand TEMimages of synthesized -MnO
2
(a), (c) and GMC (b), (d).
In order to further characterize the structure of the as synthe-
sized materials, FTIR analyses of GO, GMC and MnO
2
were carried
out and the corresponding spectra are shown in Fig. 4. In the spec-
trum of GO, a broad absorption band at 3446cm
1
is observed,
which corresponds to the O H stretching vibration [30], while
the absorption band at 1722cm
1
can be assigned to the typi-
cal stretching vibrations of carbonyl and carboxyl groups. Another
absorption band at 1624cm
1
can be attributed to the vibration
of the adsorbed water molecules and aromatic C C [21]. The weak
peaks around1050to 1250imply the presence of C O. Onthe other
hand, in the spectrum of MnO
2
, the absorption bands at 513, and
Fig. 2. XRD patterns of -MnO
2
and GMC.
702cm
1
are assigned to the vibration of Mn O bond in a MnO
6
octahedra framework, which presents a clear signature that can be
used for probing the -MnO
2
type materials [31,32]. In the spec-
trum of GMC, a similar pattern as -MnO
2
was shown. Although
most of the absorption bands of GO are overlapped with those of
-MnO
2
, the much diminished broad band around 1200cm
1
is an
important evidence proving the partial reduction of GO.
Partial reduction of GO by hydrothermal treatment was further
supported by Raman spectroscopy on GO, GMC, and reduced GO
(RGO) which was prepared with the same hydrothermal process
as for the preparation of GMC but without MnO
2
as a control for
Fig. 3. TGA curves of the synthesized GMC.
468 Y. Zhang et al. / Electrochimica Acta 108 (2013) 465471
Fig. 4. FTIR spectra of GO, -MnO
2
and GMC.
comparison. In Raman spectroscopy of carbon materials such as
GO and graphene, two rst-order Raman spectra of the samples
are observed. The band at around 1350cm
1
(D-band) originates
from atomic displacement and disorder induced features caused
by lattice defects, distortion or nite graphene size, while the band
at around 1580cm
1
(G-band) indicates the formation of well-
graphitized carbon [33]. Then, as for graphene, the intensity ratio
of D-band to G-band (I
D
/I
G
) is generally used to assess their crys-
tallinity andchemical structure. FromFig. 5, it canbe seenthat I
D
/I
G
of GOdecreasedfrom0.93to0.78after the hydrothermal treatment
Fig. 5. Raman spectra of GO, RGO and GMC.
on MnO
2
and GO, like the case of RGO. A decreased I
D
/I
G
reects an
increase in the average size of the sp
2
domains and this indicates
a reduction of GO [34]. This notable decrease in I
D
/I
G
conrms that
the GO has been reduced during the hydrothermal process.
The oxygen containing functional groups reduction and simul-
taneous transformation of the GO to RGO can be explained by
dehydration of GO. The edges of as-synthesized GO, as well as
some parts of its basal plane, are terminatedby hydrogen, hydroxyl,
ether, and carboxylic groups. When hydroxyl groups and hydrogen
atoms are attached to two neighboring carbons, they could com-
bine through dehydration reaction resulting in the formation of
Fig. 6. First two dischargecharge curves of (a) -MnO
2
and (b) GMC between 0.01 and 3V (versus Li/Li
+
). Cyclic voltammetry curves of (c) -MnO
2
and (d) GMC electrode
at a scan rate of 0.1mVs
1
.
Y. Zhang et al. / Electrochimica Acta 108 (2013) 465471 469
H
2
Oand reduction of GOin an acidic environment [34]. If an epoxy
group is attached to carbon atoms of graphene with two hydrogen
atoms attached to the neighboring carbons in an acidic environ-
ment the system will rst hydrate, transforming the epoxy group
( O ) to two hydroxyl groups, which then reduce to H
2
O and RGO
with sp
2
-bonded carbon atoms [35]. In the case of intramolecular
dehydration, the elimination of OH

and H
+
can occur on the edge
sites of G, followed by the recovery of -bonding.
As for the composition of MnO
2
and RGO, similar dehydrations
arise between nanowires and GO. As seen from Fig. 4, hydroxyl
group were observed from-MnO
2
nanowires synthesized by our
hydrothermal route consisting with others reports [36]. Hence,
these hydroxyl group could react with hydrogen atoms located at
the edge and basal plane of GO forming the GMC materials.
3.2. Electrochemical and cell performance
To characterize the electrochemical performance of GMC and
pure MnO
2
nanomaterials in LIBs, cyclic voltammograms (CVs)
and the rst two dischargecharge (DC) proles of pure MnO
2
and GMC were obtained and studied. Fig. 6a and b shows the rst
two dischargecharge curves of -MnO
2
and GMC electrodes at a
current density of 60mAg
1
. During the rst discharge process, -
MnO
2
and GMC present a long voltage plateau at about 0.4V and
then the plateau decreases slowly to 0.01V corresponding to the
formationof a solidelectrolyte interface (SEI) layer [37]. For the ini-
tial charge curve as shown in Fig. 6a, the slope in voltage between
1.0 and 1.5Vis anindicator of typical characteristic of voltage trend
of MnO
2
electrode, but the electrochemical oxidation of GMC elec-
trode may proceed in two steps since two slopes are observed at
1.3V and 2.1V. The voltage plateaus for the rst two DC proles
shown in Fig 6a and b are consistent with the redox peaks of CV
curves of -MnO
2
and GMC electrodes, in Fig. 6c and d, respec-
tively. Intherst cycle, acathodic peakaround0.30.4Vis observed
in both -MnO
2
and GMC respectively, which can be assigned to
the electrochemical reduction reaction of MnO
2
with Li, which is
described by MnO
2
+4Li
+
+4e

Mn
(0)
+2Li
2
O and the formation
of SEI layer witha reversible polymer/gel like lm[38,39]. The main
anodic peaks observed at 1.3V from -MnO
2
, and 1.3V and 2.1V
fromGMC are ascribed to the oxidation reaction of Mn
(0)
to Mn
(4+)
[40] and the decomposition of the polymer/gel layer at high oxi-
dation potential above 2.0V [38], which are both consistent with
our previous observation from the discharge-charge curves. Fur-
thermore, the rst discharge capacities of both MnO
2
and GMC
electrodes are larger thantheoretical capacities (1232mAh g
1
) [1],
which corresponds to the decomposition of electrolyte and forma-
tion of SEI layer on the surface of the electrode and further lithium
storage via interfacial charging at metal/Li
2
O interface.
Fig. 7a presents the result of cycling performance. The discharge
capacity of GMC, which is calculated including both graphene
and MnO
2
, was kept at 998mAh g
1
up to 30 cycles, while
the capacity of MnO
2
decreased to below 200mAh g
1
. In the
GMC, the graphene content is 14% as discussed above. Hence
the contribution of graphene to total capacity of the GMC is
about 104.16mAh g(GMC)
1
considering the theoretical capacity
of graphene (744mAh g
1
) [41]. In another word, only around 10%
of the capacity is provided by graphene, which accounts for 14%
of GMC in weight. Therefore, the superior capacity is mainly con-
tributed by MnO
2
. The capacity reduction of MnO
2
is likely due to
the loss of electrical contact between the particles caused by the
large volume change during Li ion insertion/extraction [1]. Fig. 7b
shows the rate capacity of the two materials at different rates,
ranging from60mAg
1
to 12Ag
1
. To conrmthe high reversible
capacity, the rate capability was examined again at 60mAg
1
after
the rate test. After several cycles, GMC electrode kept stable capac-
ity even at high rates of 12Ag
1
(about 590mAh g
1
). The good
Fig. 7. (a) Cycling performance of GMC and -MnO
2
electrode at 60mAg
1
rate. (b)
Capacity of GMC and -MnO
2
electrode at different current rate from60mAg
1
to
12Ag
1
with respect to the cycle number.
electrochemical performance of GMC results from the combined
advantages of the 3D network structure and the porous carbon
coating layer.
To understand the observed outstanding capacity and rate
performance of GMC, BET and electrochemical impedance spec-
troscopy were performed. BET test shows that the surface area
of the nanowires increased from37.7m
2
g
1
to 110.7m
2
g
1
after
graphene coverage. It indicates that the graphene coating could
inhibit agglomeration of MnO
2
nanowires, leading to an increased
surface area. Besides, graphene coating onMnO
2
canact as aneffec-
tive conductive matrix as proved with EIS analysis. EIS has been
recognized as one of the principal methods examining the fun-
damental behavior of electrode materials for LIBs. An impedance
spectrumis usually a composite curve consisting of an arc at higher
frequency region and a spike at lower frequency region [42]. The
impedance spectra of GMC and -MnO
2
were analyzed and t-
ted to the equivalent circuit as shown in Fig. 8. In the equivalent
circuit, R1 is the total resistance of electrolyte, electrode and sep-
arator. R2 and CPE1 are the resistance and capacitance of the lm
formed on the electrode surface, which is related to the formation
of SEI. R3 and CPE2 correspond to the charge transfer resistance
and the double-layer capacitance on the grain surface, respec-
tively. W1 is known as the Warburg resistance and is related to
the frequency dependence of ion diffusion/transportation in the
electrolyte to the electrode surface. The tting values from this
equivalent circuit are presented in Table 1. It is evident that the
GMC electrode has a much lower electrolyte resistance and charge
470 Y. Zhang et al. / Electrochimica Acta 108 (2013) 465471
Fig. 8. EIS results of the GMC and -MnO
2
.
Table 1
Kinetic parameters of the electrodes.
Sample R1 () R2 () R3 () CPE1 (F) CPE2 (F)
GMC 3.50 7.21 36.69 1.1510
5
2.3010
5
-MnO
2
6.66 9.52 61.90 7.1110
6
1.4410
5
transfer resistance (R1=3.50, R3=36.69) than those of the pristine
MnO
2
(R1=6.66, R3=61.90). It conrms that the graphene coating
can endow the electrode with a high conductivity and this greatly
enhances electron transport during the electrochemical lithium
insertion/extraction. Further, the 3D conductive network offered
withthegraphenecoverageplays another crucial roleas conductive
buffer layers to maintain electrical contacts with MnO
2
nanowires
even after the large volumetric change during lithiation or delithi-
ation. The electrically conductive graphene not only imparts high
electron transport properties but also maintains the intact struc-
ture of MnO
2
nanowires within the electrode. Additionally, the 3D
network structure can potentially improve Li ion mass diffusion
into active sites.
As revealed and discussed, the effects displayed after graphene
coating on MnO
2
nanowires including: (i) increased surface area,
(ii) lower electrolyteandchargetransfer resistances, and(iii) ability
to absorb volumetric change during lithiation and delithiation, are
believed to be the main reasons behind the much improved rate
capability and cycle stability of GMC. And all these can be achieved
through a facile and green hydrothermal approach that completes
GOreduction and composition formation simultaneously. The ease
of preparation, together with the superior characteristics displayed
fromtheGMC prepared, thegreenhydrothermal approachreported
here is a viable and useful technique to achieve high performance
LIB with GMC as anode material.
4. Conclusions
We proved that synthesizing of GMC from GO and MnO
2
nanowires using a hydrothermal route in which GOcan be reduced
and coupled with MnO
2
at the same time is a facile and ecolog-
ical way of manufacturing graphenemetal oxide nanocomposite.
Undesired agglomeration of MnO
2
nanomaterials usually observed
for the preparation of grapheneMnO
2
composite can be avoided
since GO is used instead of graphene in the mixing process. Fur-
ther, the graphene coating in GMC was shown to signicantly
increase the electrode surface area, greatly improve the electrical
characteristics and avoid electrode breakdown due to volumetric
expansion or contraction during lithiation and delithiation. As an
anode material for LIBs, GMC exhibits excellent electrochemical
properties with long-cycling capacity and high-rate performance.
It is a promising material that could be further explored as high
capacity anode material for LIB application.
Acknowledgements
The authors appreciate the support of the Science and Tech-
nology Foundation of China Academy of Engineering Physics (No.
2012B0302041). We are indebted to Magaret Yau, Jiahui Lin,
Jicheng Zhang, Gucheng Long and Dr. Meikun Fan for their kind
help and fruitful discussions.
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