Electrochimica Acta 176 (2015) 103–111

Contents lists available at ScienceDirect

Electrochimica Acta
journal homepage: www.elsevier.com/locate/electacta

3D Nanostructured Molybdenum Diselenide/Graphene Foam as

Anodes for Long-Cycle Life Lithium-ion Batteries
Jianyu Yaoa,b , Borui Liuc , Sehmus Ozdenb , Jingjie Wub , Shubin Yangd,
Marco-Tulio F. Rodriguesb , Kaushik Kalagab , Pei Dongb , Peng Xiaoe , Yunhuai Zhanga,* ,
Robert Vajtaib , Pulickel M. Ajayanb,*
a
College of Chemistry and Chemical Engineering, Chongqing University, Chongqing 400044, PR China
b
Department of Materials Science and NanoEngineering, Rice University, 6100 Main Street, Houston, TX 77005, USA
c
Department of Mechanical Engineering, The University of Texas at Austin, Austin, Texas 78712, United States
d
School of Materials Science and Engineering, Beihang University, Beijing, PR China
e
College of Physics, Chongqing University, Chongqing 400044, PR China

A R T I C L E I N F O A B S T R A C T

Article history: A self-assembled MoSe2 nanolayers/reduced graphene oxide (MoSe2/rGO) foam was prepared using a
Received 22 April 2015 hydrothermal method. The samples were systematically investigated by X-ray diffraction, field emission
Received in revised form 22 June 2015 scanning electron microscopy, energy dispersive X-ray spectroscopy, and high-resolution transmission
Accepted 29 June 2015
electron microscopy. Electrochemical performances were evaluated in two-electrode cells versus
Available online 2 July 2015
metallic lithium. It is demonstrated that the obtained MoSe2/rGO nanocomposites show three-
dimensional architecture and excellent electrochemical performance as anode materials for Li-ion
Keywords:
batteries. The specific capacity of MoSe2/rGO anode can reach up to 650 mAh g
1 at a current rate of 0.1C
Graphene
MoSe2 nanolayers
in the voltage range 0.01–3.0 V (vs. Li/Li+), which is higher than the theoretical capacity of MoSe2
Synergistic effect (422 mAh g
1). Additionally, the fabricated half cells have shown good rate capability and long cycling
Lithium-ion battery stability with 10.9% capacity loss after 600 cycles under a current density of 0.5C. The excellent
Long-cycle life performance of the synthesized MoSe2/rGO is attributed to its unique nanostructure, including
nanolayered MoSe2, highly conductive rGO networks and mechanically stable 3D architecture.
ã 2015 Elsevier Ltd. All rights reserved.

1. Introduction Molybdenum diselenide (MoSe2), which belongs to the family

Nowadays, lithium-ion batteries (LIBs) have become the most
favorite rechargeable batteries among all the existing battery
systems [1–3]. To develop LIBs of high capacity and long lifetime,
extensive researches are being performed to develop new anode
materials [4]. Si- and Ge-based anode materials have attracted
tremendous attentions owing to their very high theoretical
capacity (4200 mAh g
1 for Si (Li4.4Si) and 1600 mAh g
1 for Ge
(Li4.4Ge)) and they are expected to significantly increase the
specific capacity and energy density of LIBs [5–9]. Unfortunately,
the large volume expansion of these materials during lithium
insertion/extraction typically results in cracking or pulverization,
thereby, causing high first irreversible capacity and rapid capacity
fading [10].
* Corresponding author.
E-mail addresses: xp2031@163.com (Y. Zhang), ajayan@rice.edu (P.M. Ajayan).
of transition metal dichalcogenides (TMDCs), is an interesting
semiconductor with a band gap of 1.1–1.5 eV [11]. It presents a
lamellar crystal structure, whose basic crystal unit is composed of
Se-Mo-Se sandwich layers. The individual layers are connected by
weak van der Waals forces, which allow atoms to insert/remove
freely between layers [12]. This unique structure makes layered
MoSe2 one of the most promising host materials for atomic
intercalations in the field of energy storage. Three-dimensional
(3D) porous nanostructures with large surface area, low mass
density and high electrical conductivity, are ideal scaffolds to
shorten diffusion length and to accommodate the volume change
[5,13–16]. 3D graphene-based frameworks such as aerogels, foams,
and sponges are an important class of new-generation porous
carbon materials, which exhibit continuously interconnected
macroporous structures, large specific surface area (theoretical
value 2630 m2 g
1) [17], and high electrical conductivity [18].
These materials can serve as a robust matrix for accommodating
metals, metal oxides, and electrochemically active polymers for
LIBs. In addition, 3D structure can potentially utilize the vertical

http://dx.doi.org/10.1016/j.electacta.2015.06.138
0013-4686/ ã 2015 Elsevier Ltd. All rights reserved.
104 J. Yao et al. / Electrochimica Acta 176 (2015) 103–111
dimension to increase the active material loading, to enhance the
interfacial kinetics and to provide sufficient space to accommodate
the stress relaxation. Therefore, it is highly desirable to utilize 3D
graphene frameworks in hybrid nanocomposites for long-cycle life,
higher rate capability and stability in lithium-ion battery anodes
compared to unstructured graphene. As previously reported, the
nanohybrid electrodes of layered metal diselenide and graphene
such as VSe2/graphene and SnSe2/graphene showed good cycle
stability and rate capability [19,20]. Nevertheless, the nanohybrid
electrodes of MoSe2 and graphene have seldom been reported.
Herein, we report a facile hydrothermal method for synthesiz-
ing a hybrid material composed of MoSe2 nanolayers grown on
reduced graphene oxide. To our best knowledge, this is the first
time that MoSe2/rGO nanocomposite used as the anode material in
lithium-ion batteries. The multilevel porous structure and high
surface area of the MoSe2/rGO nanocomposites improve the
conductivity and shorten lithium-ion path length during the
lithium insertion/extraction process. These advantageous charac-
teristics of the advanced 3D hierarchical structures could lead to
higher capacity and longer cyclability compared to pristine MoSe2
or rGO.
2. Experimental
2.1. Synthesis of GO and MoSe2 precursor
Graphene oxide (GO) nanosheets were synthesized from
commercial graphite (SP-1 graphite, purchased from Bay Carbon
Corporation) according to a modified Hummers method described
elsewhere [21]. 8 mmol of Se powder (
100 mesh,  99.99%) was
dissolved in 10 mL hydrazine hydrate (N2H4H2O, 50–60%)
solution, followed by constant magnetic stirring for 12 h. In a
separate flask, 4 mmol of Na2MoO42H2O (sodiummolybdate
dihydrate) was dispersed in 40 mL distilled water under constant
magnetic stirring. Then 10 ml hydrazine hydrate-Se was slowly
added to 40 ml Na2MoO4 solution at room temperature. Finally the
mixed MoSe2 precursor gave a clear dark brown solution with the
Mo:Se mole ratio close to 1:2.
Fig. 1. (a) Schematic illustration of the synthetic process of 3D structured MoSe2/rGO nanocomposite. (b) Photographs of the fabrication of MoSe2/rGO nanocomposite.
2.2. Synthesis of MoSe2/rGO
The MoSe2/rGO hybrid was synthesized by a simultaneous
hydrothermal synthesis and an assembly procedure. In a typical
procedure, 2 mL MoSe2 precursor was mixed with 10 mL GO
solution (2 mg mL
1) and sonicated for 1 hour. Then the resulting
mixture was sealed in a Teflon-lined stainless steel autoclave
(100 mL) and was hydrothermally treated at 200  C for 24 h. After
cooling to room temperature, the product was washed thoroughly
with deionized water and ethanol several times, and freeze-dried
to preserve the 3D architectures. As a reference, pristine MoSe2 and
rGO were also prepared under the same experimental conditions.
2.3. Materials characterization
The morphology and microstructure of the obtained 3D
structured MoSe2/rGO nanocomposites were systematically per-
formed by scanning electron microscope (FE-SEM, JEOL 6500),
transmission electron microscope (TEM, JEOL 2010), X-ray
diffraction (XRD, Rigaku D/Max Ultima II Powder X-ray diffrac-
tometer) and energy dispersive X-ray spectroscopy (EDX, FEI
Quanta 400 ESEM FEG). X-ray photoelectron spectroscopy (XPS)
was carried on PHI Quantera X-ray photoelectron spectrometer
with a chamber of 510
9 torr and monochromatic aluminum Ka
X-rays, and the obtained data was analyzed with the MultiPak
software. The mass ratio of MoSe2 in MoSe2/rGO was calculated by
the weight loss of 25–700  C from the TGA analysis (Thermo-
gravimetric Analysis, Q-600 Simultaneous TGA/DSC) with a
heating rate of 10  C min
1 in air. Nitrogen adsorption isotherms
and the Brunauer-Emmett-Teller (BET) surface area were mea-
sured at 77 K with a Quantachrome Autosorb-3B analyzer (USA).
2.4. Electrochemical measurements
The electrochemical measurements were performed using
CR2032 coin-type cells: the working electrodes were prepared
by mixing our samples and polyvinylidene fluoride (PVDF) as
binder in a weight ratio of 90:10 using n-Methyl-2-pyrrolidone
 J. Yao et al. / Electrochimica Acta 176 (2015) 103–111 105

(NMP) as the solvent. The mixture were stirred into a homoge-
neous slurry. Then the obtained slurry was coated onto a pure
copper foil (99.6%, Goodfellow) and dried in a vacuum oven at 85  C
for 12 h. Lithium metal foil (Alfa Aesar) was used as a counter
electrode. The liquid electrolyte used was 1 M LiPF6 in a 1:1 v/v
mixture of ethylene carbonate (EC) and diethyl carbonate (DEC)
(Solvionic, France, battery grade). The cells were assembled in an
argon-filled glovebox with the concentrations of moisture and
oxygen below 0.1 ppm. CV curves were recorded on an Arbin BT-
2000 battery station at a scanning rate of 0.1 mV s
1 at room
temperature. The electrochemical performance measurements
were carried out on a LAND CT2001A battery system tester at
various current rates in the voltage range of 0.01–3.0 V. The
impedance spectra were recorded on an Autolab workstation
(PGSTAT302N) by applying a sine wave with amplitude of 5.0 mV
over the frequency range from 100 kHz to 0.01 Hz.

Fig. 2. (a) TGA and (b) XRD patterns of MoSe2/rGO, pristine MoSe2 and rGO.

Fig. 3. Characterization of the morphology of pristine MoSe2 and MoSe2/rGO nanocomposite. (a, b, c) Typical SEM and TEM images of pristine MoSe2; (d, e, f) Typical SEM and
TEM images of MoSe2/rGO, revealing that the MoSe2 nano-layer changed the structure of the graphene sheets.
106 J. Yao et al. / Electrochimica Acta 176 (2015) 103–111
3. Results and discussion
The synthetic process of 3D structured MoSe2/rGO foam is
described in Fig. 1. Firstly, MoSe2 precursor was adsorbed on the
surface of GO sheets by the functional groups (e.g., –OH, –COOH) of
GO (as shown in Fig. 1a). The mixed solution turned clear dark
brown (Fig. 1b) and the MoSe2 precursor was well-dispersed in the
GO solution homogeneously after 1 h sonication. Next, MoSe2
nanosheets were formed and embedded on graphene films in the
process of hydrothermal treatment. Simultaneously, the insulating
GO was reduced into conductive rGO. Then, 3D porous solid
structure was formed after freeze-drying.
Fig. 2a presents the thermogravimetric analysis (TGA) of the
MoSe2/rGO, pristine MoSe2 and rGO, which were carried out from
25 to 700  C with a heating rate of 10  C min
1 in air. The weight
fraction (wt.%) of MoSe2 is 35% in the MoSe2/rGO nanocomposites.
Fig. 2b displays the XRD patterns of rGO, MoSe2/rGO and MoSe2. At
around 26 , there is a wide diffraction peak, which can be
attributed to the (002) plane of rGO. The peak is invisible in the
MoSe2/rGO sample, indicating that rGO flakes are well-separated
by numerous MoSe2 nanolayers. The other XRD peaks at 14.2 ,
26.7, 36.5 , 43.9 , 56.1 and 73.4 are attributed to the diffractions
of (002), (100), (102), (006), (110) and (200) faces of the monoclinic
MoSe2 (JCPDS: 77-1715), indicating the crystalline nature of the
prepared material [22,23].
Scanning electron microscopy (SEM) and transmission electron
microscopy (TEM) reveal the typical structures of the pristine
MoSe2 and MoSe2/rGO (Fig. 3). Fig. 3a, b show that the pristine
MoSe2 possesses a flower-like structure. The TEM image in Fig. 3c
Fig. 4. XPS survey spectra of pristine MoSe2 and MoSe2/rGO. (a) Full XPS survey spectrum. (b) C 1s core-level XPS. (c) Mo 3d core-level XPS. (d) Se 3d core-level XPS.
demonstrates that the flower-like structure is composed of ultra-
thin nanosheets, which appear to have rich folded edges exhibiting
few-layered structures. The porous structure with atomically thin
sheets indicates that the scaffold is built of stacked graphene
nanosheets. The MoSe2 nanolayers are not readily observable from
the SEM images (Fig. 3d, e), suggesting that the dispersion of MoSe2
on rGO should be relatively uniform. The high magnification TEM
image (Fig. 3f) shows several MoSe2 stripe-like lines on rGO
demonstrating that the nanosheets consist of 6-12 Se-Mo-Se layers
as counted on the graphene faces. Note that the number of layers
was estimated from over 50 images. The distance between
adjacent layers is ca. 0.60 nm, almost same as the reported data
(0.62 nm) for the (002) planes of MoSe2, which is consistent with
the results obtained from the XRD pattern [23,24]. This further
supports the argument that the MoSe2 layers vertically along the
curved rGO surface.
The compositions of the MoSe2/rGO nanocomposites were
further characterised using X-ray photoelectron spectroscopy
(XPS). As shown in the XPS data (Fig. 4a), the main elements in
the MoSe2/rGO nanocomposites are C, O, Mo and Se. According to
the high-resolution C1s XPS spectrum (Fig. 4b), a number of
functional groups were founded on the graphene sheets, such as
hydroxyl (C–OH) and carboxyl (–COOH) groups, which might form
covalent bonding, hydrogen bonding or van der Waals interaction
with MoSe2 and enable direct growth of MoSe2 on the graphene
sheets. In the Mo 3d XPS region (Fig. 4c), Mo 3d5/2 and Mo 3d3/2
were found at 231.5 and 228.3 eV, confirming that molybdenum is
in its Mo (IV) state. Se 3d5/2 and Se 3d3/2 located at 54.2 and 55.0 eV
in Fig. 4d are attributed to the oxidation state of
2 for Se in MoSe2.
 J. Yao et al. / Electrochimica Acta 176 (2015) 103–111
Fig. 5. Elemental mapping images of the MoSe2/rGO foam. (a) SEM image and corresponding EDX maps of (b) carbon, (c) oxygen, (d) molybdenum, (e) selenium and (f) EDX
spectrum of the nanocomposite in oxygen in the selected area, indicating the homogeneous dispersion of molybdenum and selenium on the rGO sheets.
The mole ratios of Mo:Se in MoSe2 and MoSe2/rGO are 1:2.11 and
1:2.05, which are close to the stoichiometry of MoSe2. To gain
further insight into the distribution of MoSe2/rGO nanocompo-
sites, we performed energy dispersive X-ray spectroscopy (EDX)
elemental mapping (Fig. 5). A typical EDX spectrum in Fig. 5f
suggests that the MoSe2/rGO hybrid is composed of C, O, Mo and Se
elements. The corresponding color maps show the homogeneous
distribution of C, O, Mo and Se throughout the entire nanostruc-
ture.
N2 adsorption-desorption analysis was measured to study the
pore structure and the specific surface area of the samples. N2
adsorption-desorption isotherms and pore size distribution curves
are shown in Fig. 6. The isotherms can be classified as type IV,
revealing the mesoporous structure of the MoSe2/rGO
Fig. 6. N2 adsorption-desorption isotherms of rGO, pristine MoSe2 and MoSe2/rGO.
The inset is the corresponding pore-size distribution curves.
107
nanocomposites. From the adsorption branch of the isotherm,
the specific surface area of rGO, pristine MoSe2 and MoSe2/rGO are
496, 33.6 and 390.1 m2 g
1 respectively, which are calculated by
the Brunauer-Emmett-Teller (BET) method (Table 1). The surface
area and pore volume of the MoSe2/rGO foam are smaller than the
rGO, which is due to the fact that many pores were blocked by
the coated MoSe2 nanolayers on the surface of graphene sheets.
The pore size distributions (inset in Fig. 6) indicate that the MoSe2/
rGO nanocomposites exhibit wide pore size distributions from
1.5 to 90 nm, further confirming the existence of mesopores and
macropores. With a large surface area, conductive rGO, and active
nanolayers of MoSe2, such a nanocomposite is beneficial for
lithium storage applications that require a sufficient interface for
electrolyte access, low contact and charge-transfer impedance, and
a short transport length for both lithium ions and electrons.
Therefore, superior lithium storage properties could be expected
for the as-prepared MoSe2/rGO nanocomposites.
The electrochemical lithium ion insertion and extraction
behavior of the MoSe2/rGO and pristine MoSe2 were investigated
by cyclic voltammetry (CV) and galvanostatic discharge-charge
cycling in the voltage range 0.01–3.0 V vs. Li/Li+. The CV curves of
MoSe2/rGO and pristine MoSe2 for the 1st, 2nd and 5th cycle at a
scan rate of 0.1 mV s
1 are shown in Fig. 7a and b. The
electrochemical reaction of MoSe2 can be estimated from that of
MoS2 because of their similar crystal structure [23]. During the
initial discharge (lithiation) process, the MoSe2/rGO displayed two
main cathodic peaks centered on ca. 1.97 and ca. 0.38 V, while the
pristine MoSe2 sample exhibits two distinct peaks locating at
1.60 and 0.70 V. The peak variation of the two samples can be
Table 1
N2 adsorption-desorption analysis results of rGO, MoSe2 and MoSe2/rGO.
Sample rGO Surface area Pore volume Average pore size (nm)
(%) (m2 g
1) (cm3 g
1)
rGO 100 496 0.88 18.9
Pristine MoSe2 – 33.6 0.06 24.5
MoSe2/rGO 35 390.1 0.67 23.6
108 J. Yao et al. / Electrochimica Acta 176 (2015) 103–111

Fig. 7. Electrochemical performances of MoSe2/rGO and pristine MoSe2. (a,b) Cyclic voltammetries of the 1st, 2nd and 5th cycle for MoSe2/rGO and pristine MoSe2 in the
voltage range from 0.01 to 3.0 V at a scanning rate of 0.1 mV s
1; Li metal was used as the counter electrode. (c,d) Galvanostatic charge-discharge curves cycled at the 1st, 2nd,
5th, 10th and 50th cycle of MoSe2/rGO and pristine MoSe2 at a current density of 0.1C. (e) Cycling performances of MoSe2/rGO, pristine MoSe2 and rGO. (f) Rate capability of
rGO, pristine MoSe2 and MoSe2/rGO electrode at different current densities. (g) Subsequent cycling tests at 0.5C for 600 cycles.

ascribed to the addition of graphene. The first cathodic peak at
1.97/1.60 V can be assigned to the insertion of Li into the interlayers
of MoSe2, accompanied by the phase transformation from the 2H
to 1T structure (CdI2 type) of LixMoSe2, i.e., from trigonal prismatic
to octahedral molybdenum coordination [25–27]. The peak at 0.38/
0.70 V is related to the reduction of MoSe2 into Mo metal particles
embedded into a Li2Se matrix and the formation of solid electrolyte
interphase (SEI) film from electrochemically driven electrolyte
degradation [28,29]. The overall reaction during this process can be
described as MoSe2 + 4Li+ + 4e
! Mo + 2Li2Se [27]. In the first
anodic sweep of the MoSe2/rGO and pristine MoSe2 sample, the
poorly defined peak located at about 1.25 V can be associated with
the partial oxidation of Mo to MoSe2, and the following obvious
peaks at around 2.16 V and 2.24 V correspond to the oxidation of
Li2Se to Se [27,30]. Thus, the electrode is mainly composed of Mo
and Se instead of the initial MoSe2 after the first cycle [31]. In the
following cathodic sweeps, the peaks at 1.97/1.60 V and 0.38/0.70 V
disappeared, and two new peaks at around 1.61/1.82 V and 1.0/
1.25 V emerged, corresponding to the conversion of Se to Li2Se and
the association of Li with Mo [27,30], respectively. From the second
cycle onwards, the CV curves of the MoSe2/rGO electrode are
almost overlapped, suggesting an excellent reversibility of the
electrochemical reaction and good cycling stability.
Fig. 7c and d shows the charge/discharge profiles of the MoSe2/
rGO and pristine MoSe2 anodes in the 1st, 2nd, 5th, 10th and 50th
cycles at a current rate of 0.1C (0.1C refers to 4 mol Li uptake into
MoSe2 per formula unit in 10 h) in the voltage range of 0.01–3.0 V.
For simplicity, the C rates of both MoSe2/rGO and MoSe2 in this
work are calculated based on theoretical capacity of MoSe2
(422 mAh g
1). As shown in the charge/discharge curves, some
plateaus are observed and are in accordance with the aforemen-
tioned CVs. The initial lithiation (discharge) capacities of the
MoSe2/rGO electrode and the pristine MoSe2 electrode are
1160 and 1430 mAh g
1, with the corresponding delithiation
(charge) capacities of 625 and 597 mAh g
1, resulting in high
initial Coulombic efficiency of 54% and 42%, respectively. The
improved performance of MoSe2/rGO may be attributed to
synergistic interactions between the rGO films and MoSe2 sheets.
 J. Yao et al. / Electrochimica Acta 176 (2015) 103–111
Fig. 8. (a) Nyquist plots of rGO, pristine MoSe2 and MoSe2/rGO obtained by applying a sine wave with amplitude of 5.0 mV over the frequency range 100 kHz–0.01 Hz. (b)
Randles equivalent circuit of the studied system. (c) SEM images of MoSe2/rGO nanocomposite electrodes after 600 cycles.
Table 2
Impedance parameters derived using equivalent circuit model for rGO, MoSe2 and
MoSe2/rGO electrodes.
Sample Re (V) Rf (V) Q1 (mF) Rct (V)
rGO 4.8 6.5 21.3 33.2
Pristine MoSe2 14.5 15.8 51.6 38.7
MoSe2/rGO 14.2 13.4 76.2 30.2
The rGO may work as mechanical buffer that alleviates the volume
change in the host matrix during charge and discharge [32].
Furthermore, the MoSe2 sheets act as a spacer that prevents the
rGO from agglomeration. Note that there may be two main
methods to improve the quite low Coulombic efficiency of the
MoSe2/rGO electrode: (1) add prelithiation treatment before
battery assembling in order to improve the conductivity and
maintain the structure of the electrode [33–35]; (2) improve the
preparation method of GO to reduce the defects on the GO basal
plane [36,37]. To highlight the critical role that graphene plays in
improving electrochemical properties of MoSe2, we compared the
cycling performances of MoSe2/rGO, pristine MoSe2 and rGO. As
shown in Fig. 7e, the capacity of MoSe2/rGO, pristine MoSe2 and
rGO after 50 cycles are 650, 480 and 340 mAh g
1, respectively.
Therefore, MoSe2/rGO with the highest specific capacity further
confirms that the addition of graphene is beneficial to the lithium
insertion/extraction and the electrochemical performances.
In addition, the rate performances of the MoSe2/rGO, pristine
MoSe2 and rGO electrodes were also tested in the cell which we
used for the above mentioned 50 cycles, as shown in Fig. 7f. The
MoSe2/rGO nanocomposite exhibited final discharge capacities of
650, 610, 530, 455 and 330 mAh g
1 at rates of 0.1, 0.2, 0.5, 1 and 2C
(30 cycles at each rate). When the current density was changed
back to 0.1C, the capacity of the MoSe2/rGO can recover up to
690 mAh g
1, revealing a good rate capability of the MoSe2/rGO
anode in a wide range of current densities. Fig. 7 g shows long-term
cycling performance and the corresponding coulombic efficiency
of the nanocomposites at a current density of 0.5C following the
109
rate performance. The discharge capacity loss of the MoSe2/rGO
nanocomposite anode is 10.9% (above 470 mAh g
1) and the
coulombic efficiency close to 100% after 600 cycles, indicating
long cycling stability. For comparison, the pristine MoSe2 and rGO
Q2 (mF) electrodes show more severe capacity fading after 150 and
43 400 cycles, respectively. This is mainly attributed to the narrow-
60 band-gap semiconducting nature and the lamellar crystal struc-
218
ture of MoSe2, whose basic crystal unit is built of Se-Mo-Se
sandwich layers, and can keep the 3D architecture of rGO after
mixing. So it can be concluded that the superior electrochemical
performance of the MoSe2/rGO anode is due to the synergistic
effect between graphene nanosheets and MoSe2 nanolayers. The
synergistic effect can be defined as that the graphene can not only
prevent the volume expansion/contraction of MoSe2 during
lithiation/delithiation, but also improve the conductive of nano-
composites. On the other hand, the MoSe2 could effectively help
avoid the interlayer accumulation of graphene [38]. Li2Se and Li2S
are believed to be intermediates during the discharge/charge
cycling [23]. Therefore, we believe that the much higher electric
conductivity of Li2Se might be largely responsible for additional
capacities, because the higher electric conductivity would be
beneficial for the conversion reaction.
To further explain why MoSe2/rGO anode exhibits such a
superior electrochemical performance compared to rGO and
pristine MoSe2 anodes, electrochemical impedance spectroscopy
(EIS) measurements were performed after 50 cycles as shown in
Fig. 8a. The Randles equivalent circuit model of the studied system
is shown in Fig. 8b according to the works reported by others [32].
Re represents the internal resistance of the test battery, Rf and CPE1
are associated with the resistance and constant phase element of
SEI film, Rct and CPE2 are assigned to the charge-transfer resistance
and constant phase element of the electrode/electrolyte interface,
ZW represents Warburg impedance corresponding to the lithium-
diffusion process. As shown in Fig. 8a, the high frequency
semicircle is attributed to the resistance Rf and CPE1 of SEI film,
the semicircle in medium frequency region is corresponding to the
charge transfer resistance Rct and CPE2 of electrode/electrolyte
110 J. Yao et al. / Electrochimica Acta 176 (2015) 103–111
interface. The straight sloping line corresponds to the lithium ion
diffusion process within bulk of the electrode material. The kinetic
differences of the three electrodes were further investigated by the
modified Randles equivalent circuit (Fig. 8b). The fitted impedance
parameters are listed in Table 2. The values of Rf and Rct of the
MoSe2/rGO anode are 13.4 V and 30.2 V respectively, which are
conspicuously lower than those of the pristine MoSe2 anode
(15.8 V and 38.7 V). This again confirms that the interconnected
rGO thin layers can increase the overall electrochemical conduc-
tivity of electrodes. To better understand the long-life performance
of the MoSe2/rGO nanosheet electrode, the MoSe2/rGO anode was
taken out from the coin cell, washed with dimethyl carbonate
solution, and the morphology of the sample was observed by SEM.
As shown in Fig. 8c, no obvious changes in the morphology are
observed for the MoSe2/rGO nanocomposites, and the graphene
membranes still keep 3D structure, demonstrating that the
structural integrity of the composite is helpful to cycling
performance. In addition, the structural stability can be ascribed
to the directly grown structure that tightly connects the graphene
nanosheets with MoSe2, preventing the detachment and agglom-
eration of the nanosheets during cycling, which finally contributes
to the long cyclability.
4. Conclusions
In summary, 3D MoSe2/rGO foam with controllable structure
was obtained via hydrothermal method. The nanocomposite
exhibits high specific capacity, long cyclability and high rate
capability. The excellent electrochemical properties can be
attributed to the synergistic effect between graphene nanosheets
and MoSe2 nanolayers. The light graphene current collector with
high electrical conductivity and stable structure accelerates the
electron transfer. The MoSe2 nanolayers embedded on reduced
graphene films shorten the transport length of lithium ions and
prevent rGO nanosheets from agglomeration, rendering the
electrode high performance. The formed 3D mesoporous structure
as a host matrix is also beneficial to lithium ions transport and
buffer the mechanical strains during lithiation/delithiation, and
shows good cycling stability. Specially, the MoSe2/rGO nano-
composite shows long cyclability with less capacity loss over
600 cycles under a current density of 0.5C. This novel structure
paves the way to design electrodes for long-cycle life LIBs.
Acknowledgements
This work was financially supported by U. S. Army Research
Office through the MURI grant (W911NF-11-1-0362) entitled,
“Atomic Layers of Nitrides, Oxides, and Sulfides” and by the
Fundamental Research Funds for the Central Universities (No.
106112015CDJZR305501). P. M. A. also acknowledges funding
sponsorship from the U.S. Air Force Office of Scientific Research for
the MURI grant (FA9550-12-1-0035) entitled, “Synthesis and
Characterization of 3-D Carbon Nanotube Solid Networks”. Y. J.Y.
gratefully acknowledges the financial support from the China
Scholarship Council (CSC) during her visit to Rice University.
References
[1] J. Dunn, L. Gaines, J. Kelly, C. James, K. Gallagher, The significance of Li-ion
batteries in electric vehicle life-cycle energy and emissions and recycling's role
in its reduction, Energy Environ. Sci. 8 (2015) 158–168.
[2] D. Larcher, J.M. Tarascon, Towards greener and more sustainable batteries for
electrical energy storage, Nat. Chem. 7 (2015) 19–29.
[3] M. Armand, J.-M. Tarascon, Building better batteries, Nature 451 (2008) 652–
657.
[4] D. Pan, S. Wang, B. Zhao, M. Wu, H. Zhang, Y. Wang, Z. Jiao, Li storage properties
of disordered graphene nanosheets, Chem. Mater. 21 (2009) 3136–3142.
[5] B. Liu, P. Soares, C. Checkles, Y. Zhao, G. Yu, Three-dimensional hierarchical
ternary nanostructures for high-performance Li-ion battery anodes, Nano Lett.
13 (2013) 3414–3419.
[6] H. Wu, G. Yu, L. Pan, N. Liu, M.T. McDowell, Z. Bao, Y. Cui, Stable Li-ion battery
anodes by in-situ polymerization of conducting hydrogel to conformally coat
silicon nanoparticles, Nat. Commun. 4 (2013) 1943.
[7] C.K. Chan, H. Peng, G. Liu, K. McIlwrath, X.F. Zhang, R.A. Huggins, Y. Cui, High-
performance lithium battery anodes using silicon nanowires, Nat.
Nanotechnol. 3 (2007) 31–35.
[8] C.K. Chan, X.F. Zhang, Y. Cui, High capacity Li ion battery anodes using Ge
nanowires, Nano Lett. 8 (2008) 307–309.
[9] D.T. Ngo, R.S. Kalubarme, H.T. Le, J.G. Fisher, C.N. Park, I.D. Kim, C.J. Park,
Carbon-interconnected Ge nanocrystals as an anode with ultra-long-term
cyclability for lithium ion batteries, Adv. Funct. Mater. 24 (2014) 5291–5298.
[10] N.-S. Choi, Y. Yao, Y. Cui, J. Cho, One dimensional Si/Sn-based nanowires and
nanotubes for lithium-ion energy storage materials, J. Mater. Chem. 21 (2011)
9825–9840.
[11] S. Tongay, J. Zhou, C. Ataca, K. Lo, T.S. Matthews, J. Li, J.C. Grossman, J. Wu,
Thermally driven crossover from indirect toward direct bandgap in 2D
semiconductors: MoSe2 versus MoS2, Nano Lett. 12 (2012) 5576–5580.
[12] Y.N. Ko, S.H. Choi, S.B. Park, Y.C. Kang, Hierarchical MoSe2 yolk–shell
microspheres with superior Na-ion storage properties, Nanoscale 6 (2014)
10511–10515.
[13] B.L. Ellis, P. Knauth, T. Djenizian, Three-dimensional self-supported metal
oxides for advanced energy storage, Adv. Mater. 26 (2014) 3368–3397.
[14] P.G. Bruce, B. Scrosati, J.M. Tarascon, Nanomaterials for Rechargeable Lithium
Batteries, Angew. Chem. Int. Ed. 47 (2008) 2930–2946.
[15] D.-l. Ma, Z.-y. Cao, H.-g. Wang, X.-l. Huang, L.-m. Wang, X.-b. Zhang, Three-
dimensionally ordered macroporous FeF3 and its in situ homogenous
polymerization coating for high energy and power density lithium ion
batteries, Energy. Environ. Sci. 5 (2012) 8538–8542.
[16] Y. Zhao, B. Liu, L. Pan, G. Yu, 3D nanostructured conductive polymer hydrogels
for high-performance electrochemical devices, Energy. Environ. Sci. 6 (2013)
2856–2870.
[17] M.D. Stoller, S. Park, Y. Zhu, J. An, R.S. Ruoff, Graphene-based ultracapacitors,
Nano Lett. 8 (2008) 3498–3502.
[18] Z.-S. Wu, Y. Sun, Y.-Z. Tan, S. Yang, X. Feng, K. Müllen, Three-dimensional
graphene-based macro-and mesoporous frameworks for high-performance
electrochemical capacitive energy storage, J. Am. Chem. Soc. 134 (2012)
19532–19535.
[19] J. Choi, J. Jin, I.G. Jung, J.M. Kim, H.J. Kim, S.U. Son, SnSe2 nanoplate-graphene
composites as anode materials for lithium ion batteries, Chem. Commun. 47
(2011) 5241–5243.
[20] Y. Wang, B. Qian, H. Li, L. Liu, L. Chen, H. Jiang, VSe2/graphene nanocomposites
as anode materials for lithium-ion batteries, Mater. Lett. 141 (2015) 35–38.
[21] W.S. Hummers Jr., R.E. Offeman, Preparation of graphitic oxide, J. Am. Chem.
Soc. 80 (1958) 1339–1339.
[22] H. Tang, K. Dou, C.-C. Kaun, Q. Kuang, S. Yang, MoSe2 nanosheets and their
graphene hybrids: synthesis, characterization and hydrogen evolution
reaction studies, J. Mater. Chem. A 2 (2014) 360–364.
[23] Y. Shi, C. Hua, B. Li, X. Fang, C. Yao, Y. Zhang, Y.S. Hu, Z. Wang, L. Chen, D. Zhao,
Highly ordered mesoporous crystalline MoSe2 material with efficient visible-
light-driven photocatalytic activity and enhanced lithium storage
performance, Adv. Funct. Mater. 23 (2013) 1832–1838.
[24] H. Wang, D. Kong, P. Johanes, J.J. Cha, G. Zheng, K. Yan, N. Liu, Y. Cui, MoSe2 and
WSe2 nanofilms with vertically aligned molecular layers on curved and rough
surfaces, Nano Lett. 13 (2013) 3426–3433.
[25] H. Liu, D. Su, R. Zhou, B. Sun, G. Wang, S.Z. Qiao, Highly ordered mesoporous
MoS2 with expanded spacing of the (002) crystal plane for ultrafast lithium ion
storage, Adv. Energy Mater. 2 (2012) 970–975.
[26] X. Zhou, L.J. Wan, Y.G. Guo, Facile synthesis of MoS2 @ CMK-3 nanocomposite
as an improved anode material for lithium-ion batteries, Nanoscale 4 (2012)
5868–5871.
[27] X. Fang, X. Yu, S. Liao, Y. Shi, Y.-S. Hu, Z. Wang, G.D. Stucky, L. Chen, Lithium
storage performance in ordered mesoporous MoS2 electrode material,
Microporous Mesoporous Mater. 151 (2012) 418–423.
[28] Y. Gong, S. Yang, L. Zhan, L. Ma, R. Vajtai, P.M. Ajayan, A bottom-up approach to
build 3D architectures from nanosheets for superior lithium storage, Adv.
Funct. Mater. 24 (2014) 125–130.
[29] Y. Gong, S. Yang, Z. Liu, L. Ma, R. Vajtai, P.M. Ajayan, Graphene-network-
backboned architectures for high-performance lithium storage, Adv. Mater. 25
(2013) 3979–3984.
[30] J. Xiao, X. Wang, X.Q. Yang, S. Xun, G. Liu, P.K. Koech, J. Liu, J.P. Lemmon,
Electrochemically induced high capacity displacement reaction of PEO/MoS2/
graphene nanocomposites with lithium, Adv. Funct. Mater. 21 (2011)
2840–2846.
[31] L. Yang, S. Wang, J. Mao, J. Deng, Q. Gao, Y. Tang, O.G. Schmidt, Hierarchical
MoS2/Polyaniline nanowires with excellent electrochemical performance for
lithium- ion batteries, Adv. Mater. 25 (2013) 1180–1184.
[32] J. Yao, Y. Gong, S. Yang, P. Xiao, Y. Zhang, K. Keyshar, G. Ye, S. Ozden, R. Vajtai, P.
M. Ajayan, CoMoO4 nanoparticles anchored on reduced graphene oxide
nanocomposites as anodes for long-Life lithium-ion batteries, ACS Appl. Mater.
Interfaces 6 (2014) 20414–20422.
[33] M.W. Forney, M.J. Ganter, J.W. Staub, R.D. Ridgley, B.J. Landi, Prelithiation of
silicon–carbon nanotube anodes for lithium ion batteries by stabilized Lithium
Metal Powder (SLMP), Nano Lett. 13 (2013) 4158–4163.
 J. Yao et al. / Electrochimica Acta 176 (2015) 103–111 111

[34] N. Liu, L. Hu, M.T. McDowell, A. Jackson, Y. Cui, Prelithiated silicon nanowires as
an anode for lithium ion batteries, ACS Nano 5 (2011) 6487–6493.
[35] Y. Wang, G. Xing, Z. Han, Y. Shi, J.I. Wong, Z. Huang, K. Ostrikov, H. Yang, Pre-
lithiation of onion-like carbon/MoS2 nano-urchin anodes for high-performance
rechargeable lithium ion batteries, Nanoscale 6 (2014) 8884–8890.
[36] D.C. Marcano, D.V. Kosynkin, J.M. Berlin, A. Sinitskii, Z. Sun, A. Slesarev, L.B.
Alemany, W. Lu, J.M. Tour, Improved synthesis of graphene oxide, ACS Nano 4
(2010) 4806–4814.
[37] C. Gomez-Navarro, M. Burghard, K. Kern, Elastic properties of chemically
derived single graphene sheets, Nano Lett. 8 (2008) 2045–2049.
[38] D. Wang, D. Choi, J. Li, Z. Yang, Z. Nie, R. Kou, D. Hu, C. Wang, L.V. Saraf, J. Zhang,
Self-assembled TiO2-graphene hybrid nanostructures for enhanced Li-ion
insertion, ACS Nano 3 (2009) 907–914.