J Nanopart Res (2017) 19: 332

DOI 10.1007/s11051-017-4019-z

RESEARCH PAPER

Carbon-based coating containing ultrafine MoO2

nanoparticles as an integrated anode for high-performance
lithium-ion batteries
Quanyi Li & Qi Yang & Yanhong Zhao & Bin Wan

Received: 4 April 2017 / Accepted: 7 September 2017 / Published online: 1 October 2017
# Springer Science+Business Media B.V. 2017

Abstract Copper-supported MoO2-C composite as an
integrated anode with excellent battery performance was
synthesized by a facile knife coating technique followed
by heat treatment in a vacuum. The obtained samples
were characterized by X-ray diffraction (XRD), Raman
spectroscopy, X-ray photoelectron spectroscopy (XPS),
thermal analysis, nitrogen adsorption and desorption
analysis, field emission scanning microscopy (FESEM),
and transmission electron microscopy (TEM). The re-
sults show the MoO2-C composite coating is comprised
of a porous carbon matrix with a pore size of 1–3 nm
and ultrafine MoO2 nanoparticles with a size of 5–
10 nm encapsulated inside, the coating is tightly at-
tached on the surface of copper foil, and the interface
between them is free of cracks. Stable PAN-DMF-H2O
system containing ammonium molybdate suitable for
knife coating technique and the MoO2-C composite
with ultrafine MoO2 nanoparticles encapsulated in the
carbon matrix can be prepared through controlling
amount of added ammonium molybdate solution. The
copper-supported MoO2-C composite coating can be
directly utilized as the integrated anode for lithium-ion
Electronic supplementary material The online version of this
article (https://doi.org/10.1007/s11051-017-4019-z) contains
supplementary material, which is available to authorized users.
Q. Li : Q. Yang (*) : Y. Zhao
School of Materials Engineering, Shanghai University of
Engineering Science, Shanghai 201620, China
e-mail: qiiyang@163.com
B. Wan
Shanghai Civil Aviation College, Shanghai 200232, China
batteries (LIBs). It delivers a capacity of 814 mA h g−1
at a current density of 100 mA g−1 after 100 cycles
without apparent capacity fading. Furthermore, with
increase of current densities to 200, 500, 1000, 2000,
and 5000 mA g−1, it exhibits average capacities of 809,
697, 568, 383, and 188 mA h g−1. Its outstanding
electrochemical performance is attributed to combined
merits of integrated anode and structure with ultrafine
MoO2 nanoparticles embedded in the porous carbon
matrix.
Keywords Molybdenum dioxide . Nanoparticle .
Carbon-based composite . Integrated anode . Energy
storage
Introduction
Lithium-ion batteries (LIBs) have been universally ac-
cepted as power resources for portable electronic de-
vices, hybrid electric vehicles, and pure electric vehi-
cles. At present, the rapid development of pure electric
vehicles calls for next generation of LIBs with higher
energy density, longer life expectancy, and faster charge
performance (Zhou et al. 2015a, b; Wu et al. 2015; Luo
et al. 2016a, b). Transition metal oxides as anode mate-
rials for LIBs have attracted considerable interest due to
their much higher theoretical capacity than the commer-
cially used graphite (Song et al. 2015; Hassan et al.
2010; Qian et al. 2013; Cao et al. 2015; Liu et al.
2016a, b; Dou et al. 2016; Qin et al. 2015a, b; Zhang
et al. 2016; Huang et al. 2016; Hou et al. 2015; Duan
332 Page 2 of 11
et al. 2012). Among them, MoO2 is considered as one of
the most promising anode materials for next-generation
LIBs because it exhibits high theoretical capacity
(838 mA h g−1), metallic conductivity
(> 1 × 104 S cm−1) and facile ion transportation property
(Zhou et al. 2015a, b; Sun et al. 2011). However, its
large volume change caused by lithium-ion insertion
and extraction will lead to cracks and pulverization that
may block its electric contact with a current collector,
and finally result in serious capacity fading (Zhou et al.
2015a, b; Sun et al. 2011).
In order to solve the problem, synthesizing MoO2
with various nano-structures was considered as an ef-
fective route. Nano-structures can not only prevent pul-
verization and cracking of electrode during discharge-
charge processes but also shorten the diffusion distance
of lithium ions (Luo et al. 2011; Zhou et al. 2015a, b;
Liu et al., 2016a, b; Gao et al. 2014). Additionally,
incorporating MoO2 with carbonaceous materials was
regarded as another effective strategy (Huang et al.
2011a, b; Ma et al. 2014; Huang et al. 2011a, b; Wang
et al. 2010). Carbonaceous materials exhibit excellent
electrical conductivity, and their volume change is
smaller than that of transition metal oxides with higher
theoretic capacity in the processes of discharge and
charge. Carbon-based composites with transition metal
oxide nanoparticles encapsulated in the carbon matrices
combine advantages of the two methods, which
achieves their excellent capacity retention. Presently,
the most common used techniques to synthesize the
carbon-based composites include solvothermal reaction
(Zhou et al. 2015a, b), hydrothermal reaction (Liu et al.
2016a, b; Gao et al. 2014), sol-gel (Li et al. 2016; Gao
et al. 2010), and electrospinning (Luo et al. 2011; Yang
et al. 2015; Kim et al. 2012; Yang et al. 2011; Yang et al.
2012a, b).
In a conventional electrode fabrication process, adhe-
sives and conductive agents are required additives to bind
electrochemical active materials on the surface of copper
foil and improve their electrical conductivity (Yu et al.
2016; Qin et al. 2015a, b; Liu et al. 2013; Tang et al.
2016; 2014). These additives usually have lower capacity
or even no capacity. Some metal oxide electrochemical
active materials have difficulty to keep close contact with
the current collector during discharge-charge processes
(Wang et al. 2014a, b). Integrated anode with electro-
chemical active materials synthesized directly on the
surface of copper foil is free of adhesives and conductive
agents, and the bonding between electrochemical active
J Nanopart Res (2017) 19: 332
materials and copper foil is tight, which leads to its high
capacity and good capacity retention. Nowadays, some
routes such as chemical vapor deposition (Wu et al.
2015), hydrothermal method (Wang et al. 2014a, b),
electrodepositing (Gu et al. 2012; Zhao et al. 2008),
and magnetron sputtering (Wu et al. 2014) have been
developed to synthesize integrated electrode.
In this study, a facile knife coating technique was
proposed to synthesize copper-supported MoO2-C com-
posite as the integrated anode with excellent battery
performance. By controlling the addition amount of
ammonium molybdate solution, the stable PAN-DMF-
H2O system containing ammonium molybdate suitable
for knife coating technique and the MoO2-C composite
with ultrafine MoO2 nanoparticles encapsulated in a
carbon matrix can be obtained.
Experimental
Synthesis of copper-supported MoO2-C composite
Mo7O24·6(NH4)·4H2O and N,N-dimethylformamide
(DMF) were purchased from Sinopharm Chemical Re-
agent Company Limited and received without further
purification. Polyacrylonitrile (PAN, MW = 45,000)
was provided by Acrylic Fibers Division of Shanghai
Petrochemical Company Limited and dried at 90 °C for
24 h before being received. In a typical procedure, 0.2 g
PAN was added into 6 g DMF to prepare 6.2 g DMF
solution of PAN after being stirred at 80 °C for 1 h; 0.2 g
Mo7O24·6(NH4)·4H2O was dissolved in 0.4-g pure wa-
ter to prepare 0.6 g aqueous solution of ammonium
molybdate with concentration of 33.3 wt%. The 0.6-g
solution of ammonium molybdate was slowly added
drop by drop into 6.2-g DMF solution of PAN under
ultrasonic vibration. The obtained milk-like stable col-
loid was knife coated on the surface of copper foil. After
being dried, the copper-supported film was sintered at
400 °C for 1 h in a vacuum with a vacuum degree of
6.67 × 10−3 Pa and a heating speed of 2 °C/min. The
obtained black coating on the surface of copper foil is
ready for the following characterization and testing.
Characterization
X-ray diffraction (XRD, X’Pect Pro MPD), Raman
spectroscopy (Raman, a Renishaw inVia), and X-ray
photoelectron spectroscopy (XPS, VG Scientific
J Nanopart Res (2017) 19: 332 Page 3 of 11 332

ESCALAB 220IXL) were employed to analyze crystal
structure and measure Raman and XPS spectra of the
MoO 2 -C composite. Thermogravimetric analysis
(TGA) and differential scanning calorimetry (DSC)
were carried out on a Mettler Toledo TGA/DSC-
type thermal analyzer in air with a heating speed of
10 °C/min and a scanning temperature range from 20
to 800 °C. Specific surface area and pore structure
analysis were conducted on an ASAP 2010 analyzer.
The MoO2-C composite was scraped from the surface
of copper foil for the tests of XRD, Raman, XPS,
TGA/DSC, and nitrogen adsorption/desorption. The
copper-supported MoO2-C composite was directly ob-
served on a Hitachi S4800 field emission scanning
microscope (FESEM). The powder scraped from the
surface of copper foil was added into ethanol and
then ultrasonically vibrated for 10 min. The obtained
black suspension was dropped on copper grids for
transmission electron microscope (TEM) observation.
Electrochemical measurement
to JCPDS 73-1249. Intensity of the three diffraction
peaks related to MoO2 is very weak, which indicates it
perhaps has poor crystallinity or ultrafine size. In the
XRD pattern, the diffraction peaks related to carbon
cannot be observed, which suggests the carbon in the
composite maybe has amorphous structure. Raman can
provide more information about amorphous carbon. The
Raman spectrum of the composite is shown in Fig. 1b.
The main peaks at 1361 and 1588 cm−1 are assigned to
E2g vibration mode of disordered carbon (D band) and
A1g vibration mode of graphite (G band), respectively
(Hassan et al. 2010). The peak intensity ratio of D band
to G band (ID/IG) is 2.21, which indicates low graphi-
tization degree of the carbon in the composite.
Because the diffraction peaks in the XRD pattern are
very weak and not obvious, XPS was performed to
further identify composition of the MoO2-C composite.
Figure 2a shows XPS spectrum of Mo3d. Two peaks at
229.34 and 232.64 eV are assigned to Mo(IV)3d5/2 and
Mo(IV)3d3/2 respectively (Baltrusaitis et al. 2015; Yoon

R-2032 coin cells assembled in an argon-filled glove

box with oxygen and water content below 1 ppm were
utilized for electrochemical performance measurement.
The copper-supported MoO2-C composite, Li foil, and
Celgard 2400 were employed as a working electrode,
counter electrode, and separator, respectively. The elec-
trolyte is comprised of 1 M LiPF6 dissolved in a mixture
of ethylene carbonate (EC), diethyl carbonate (DEC),
and ethyl methyl carbonate (EMC) with a volume ratio
of 1:1:1 containing 2 vol% vinylene carbonate (VC).
Specific capacity, cyclic, and rate performance tests
were carried out on a Neware-CT3008 instrument with
a voltage range from 0.01 to 3.0 V. Cyclic voltammetry
(CV) measurement with a scanning rate of 0.1 mV s−1
and a voltage range from 0.01 to 3.0 V and electrochem-
ical impedance spectroscopy (EIS) measurement with
signal amplitude of 5 mV and a frequency range from
0.01 to 106 Hz were conducted on a CHI660A electro-
chemical workstation.

Results and discussion

Figure 1a shows XRD pattern of the MoO2-C compos-

ite. The only three diffraction peaks at 2θ = 26.04°,
37.08 °, and 53.57 ° can be indexed to (110), (211),
and (022) planes of monoclinic MoO2 phase according Fig. 1 MoO2-C composite. a XRD pattern. b Raman spectrum
332 Page 4 of 11
Fig. 2 MoO2-C composite. a XPS spectrum of Mo3d. b XPS
spectrum of C1s
et al. 2012). In Fig. 2b, the XPS spectrum of C1s can be
fitted into two peaks at 284.85 and 286.36 eV which are
attributed to graphitic carbon and disorder carbon, re-
spectively (Yang et al. 2011; Yang et al. 2012a, b).
Therefore, through analysis of XRD, Raman, and XPS,
it can be concluded that the MoO2-C composite consists
of monoclinic MoO2 and low graphitization carbon.
Figure 3a, b demonstrate top-view and cross-
sectional FESEM images of the copper-supported
MoO2-C composite. It can be seen some MoO2
nanoparticles are exposed on the surface of the car-
bon matrix (Fig. 3a) and the coating attaches tightly
on the surface of copper foil without any cracks at
their interface (Fig. 3b). TEM observation can pro-
vide more detail about the micro-structure of the
MoO2-C composite. From its TEM image, as pre-
sented in Fig. 3c, it can be observed many ultrafine
MoO2 nanoparticles with a size of 5–10 nm are
J Nanopart Res (2017) 19: 332
encapsulated in the carbon matrix and the composite
displays a porous structure with a pore size of 1–
3 nm. Some metal oxide-carbon composites demon-
strate similar phenomenon (Yang et al. 2015; Kim
et al. 2012; Jung and Lee 2011). Although most
metal oxide nanoparticles are encapsulated in the
carbon matrix, but some metal oxide nanoparticles
are inevitably exposed on the surface of the carbon
matrix. Figure 3d shows HRTEM image of the
MoO2-C composite. From lattice fringes of a nano-
particle, it can be seen its interplanar spacing is
0.34 nm which corresponds to (110) plane of mono-
clinic MoO2 (JCPDS 73-1249). In the HRTEM im-
age, the lattice fringes are not clear, which suggests
MoO2 nanoparticles have poor crystallinity.
Thermal analysis is conducted to test carbon con-
tent of the composite. Its result is presented in Fig. 4.
Its TGA curve exhibits five weight loss stages: (1)
from 20 to 100 °C, the weight loss of 6% is attrib-
uted to evaporation of physically adsorbed water;
(2) from 100 to 400 °C, the weight loss of 5% is
assigned to evaporation of residual chemically
adsorbed water; (3) from 400 to 580 °C, the weight
loss of 46.5% is related to synthetic effect of oxida-
tion of carbon to CO2 and Mo4+ to Mo6+; (4) from
580 to 710 °C, its weight remains stable; and (5)
from 710 to 800 °C, its weight loss of 14.5% is
attributed to sublimation of MoO3. The theoretical
value of the weight increase from MoO2 to MoO3 is
12.5% (Zeng et al. 2013), so the carbon content in
the MoO2-C composite is evaluated to be about
34 wt%. In its DSC curve, the exothermic peak
between 400 and 580 °C is attributed to synthetic
thermal effect of oxidation of carbon to CO2 and
Mo4+ to Mo6+; the endothermic peak at 783 °C is
assigned to sublimation of MoO3.
Figure 5 and its inset show nitrogen adsorption-
desorption isotherm and pore size distribution curve of
the MoO2-C composite, respectively. The nitrogen ad-
sorption and desorption isotherm is IV type with H3
type hysteresis loop which is a result of nitrogen adsorp-
tion and desorption behavior of slit-shaped micro-pores.
Its specific surface area and total pore volume are
14.33 m2 g−1 and 0.014 cm3 g−1, respectively. Its pore
size is concentrated at 1–3 nm which is in agreement
with the TEM result shown in Fig. 3c, d.
Formation of stable colloid containing precursors
of metal oxides is important for the knife coating
technique to prepare homogenous metal oxide-
J Nanopart Res (2017) 19: 332 Page 5 of 11 332

Fig. 3 Copper-supported MoO2-

C composite coating. a Top-view
FESEM image. b cross-sectional
FESEM image. MoO2-C
composite. c TEM image. d
HRTEM image

carbon composites. Figure 6 demonstrates the typi-
cal formation process of the stable PAN-DMF-H2O
system containing ammonium molybdate. Because
H2O is compatible with DMF and incompatible with
PAN, the addition of H2O into DMF solution of
PAN will cause desolvation effect. As addition
amount of H2O increases, PAN chains tend to curl,
and then gradually precipitate from DMF solution,
and finally agglomerate to form PAN bulks
(Prahsarn et al. 2011; Yu et al. 2010). The addition
amount of H2O and adding H2O speed are crucial
for the formation of the stable PAN-DMF-H2O sys-
tem. In the experiment, in order to form stable
colloid, the aqueous solution of ammonium molyb-
date was slowly added dropwise into the DMF so-
lution of PAN under constant ultrasonic vibration to
prevent PAN in DMF solution from precipitation.

Fig. 5 Nitrogen adsorption-desorption isotherm and pore size

Fig. 4 TGA and DSC curves of the MoO2-C composite distribution curve of the MoO2-C composite
332 Page 6 of 11 J Nanopart Res (2017) 19: 332

As the amount of added ammonium molybdate so-

lution increases to 1.2 g, enlargement of MoO 2
nanoparticle size and the agglomeration of MoO2
nanoparticles can be observed (Fig. S2).
In the discharge-charge processes, the electro-
chemical reactions of the MoO2-C composite elec-
trode can be illustrated by the following three equa-
tions (Zeng et al. 2013):

xLiþ þ xe− þ MoO2 ⇔Lix MoO2 ð0 ≤ x ≤ 0:98Þ ð1Þ

Li0:98 MoO2 þ 3:02Liþ ⇔2Li2 O þ Mo ð2Þ

xLiþ þ CðamorphouscarbonÞ þ xe− ⇔Lix C ð3Þ

Fig. 6 Schematic diagram showing formation of stable PAN-
DMF-H2O system containing ammonium molybdate Figure 7a shows the first three CV curves of the MoO2-
C composite electrode. For the first cycle, the reduction
However, excessive added water will inevitably
cause PAN precipitation. Fig. S1 shows the photo-
graphs of the PAN-DMF-H2O system containing
ammonium molybdate prepared by 0.6, 1.2, and
1.8 g added ammonium molybdate solution, and
the films formed by knife coating them on the sur-
face of copper foils. All obtained suspensions are
milk like (Fig. S1a, Fig. S1b, and Fig. S1c). Only
the PAN-DMF-H2O system containing ammonium
molybdate prepared by 0.6 g added ammonium mo-
lybdate solution forms uniform film on the surface
of copper foil (Fig. S1d). As the amount of added
ammonium molybdate solution increases to 1.2 and
1.8 g, some white flakes appear on the surface of the
formed films, which suggests the production of PAN
precipitation (Fig. S1e and Fig. S1f).
In the subsequent sintering process, the PAN is
carbonized to form the carbon matrix; the ammoni-
um molybdate is thermally decomposed to form
MoO2. For the PAN-DMF-H2O system containing
ammonium molybdate prepared by 0.6 g added am-
monium molybdate solution, the ammonium molyb-
date transforms to ultrafine MoO2 nanoparticles with
a size of 5–10 nm as shown in Fig. 3c, d. The
carbon matrix is beneficial to the formation of ultra-
fine MoO2 nanoparticles because carbon matrix can
prevent MoO2 nanoparticles from agglomeration. Fig. 7 MoO2-C composite electrode. a Cyclic voltammograms of
Perhaps, the micro-pores in the MoO2-C composite the first three cycles. b The discharge-charge curves of the first
are the result of pyrolysis of ammonium molybdate. three cycles
J Nanopart Res (2017) 19: 332 Page 7 of 11 332

peak at 0.65 V is attributed to the formation of solid 739 mA h g−1 after 100 cycles, which perhaps is
electrolyte interphase (SEI) layer on the surface of the related to enlargement of MoO2 nanoparticle size
electrode (Zeng et al. 2013; Gao et al. 2014). This peak and the agglomeration of MoO2 nanoparticles as
is only observed in the first cycle, but not in the subsequent presented in Fig. S2. The capacity of the pure
cycles, which suggests the irreversible electrochemical MoO2 fades very quickly, which suggests the carbon
reaction related to the formation of SEI layer has matrix plays an important role for MoO2 based an-
completely finished in the first cycle and the formed SEI ode materials with high electrochemical perfor-
layer is stable. The reduction peak at 0.02 V is assigned to mance. The pure carbon coating delivers a capacity
lithium-ion insertion into carbon (Yang et al. 2015). Mean- of 348 mA h g−1 and good capacity retention. For
while, the oxidation peak observed at 0.2 and 1.4 V can be the MoO2-C composite electrode, MoO2 provides
attributed to lithium-ion extraction from carbon (Yang capacity of 553 mA h g−1 (838 mA h g−1*66%)
et al. 2015) and phase transformation of the LixMoO2 and carbon provides capacity of 118 mA h g −1
from orthorhombic to monoclinic respectively (Yoon (348 mA h g−1*34%). Its extra capacity maybe orig-
et al. 2012; Zeng et al. 2013). The CV curves of the second inates from its porous structure and nano-structure.
and the third cycles are nearly overlapping with each other, The rate capability of the MoO2-C composite elec-
indicating the MoO2-C composite coating and the inte- trode is investigated by stepwise increasing the
grated electrode have good stability and reversibility for
the insertion and extraction of lithium ions. The reduction
peak at 1.15 V of CV curves of the second and the third
cycles is related to the phase transformation of LixMoO2
from monoclinic to orthorhombic (Yoon et al. 2012; Zeng
et al. 2013).
Figure 7b presents discharge-charge curves of the
MoO2-C composite electrode in the initial three
cycles at a current density of 100 mA g−1 and a
potential range from 0.01 to 3 V. It is observed that
it delivers discharge and charge capacities of 1342
and 959 mA h g−1 respectively in the first cycle,
which means its initial coulombic efficiency is
71.44%. The 28.56% capacity loss is attributed to
the irreversible electrochemical reaction related to
formation of SEI layer. In the second and third
cycles, the coulombic efficiency increases to 98.53
and 99.17%, which implies irreversible electrochem-
ical reaction related to formation of SEI layer has
almost finished during the first cycle.
Figure 8a demonstrates the cyclic performance of
the MoO2-C composite electrode, pure carbon coat-
ing prepared by carbonization of PAN and pure
MoO2 prepared by thermal decomposition of ammo-
nium molybdate. The MoO2-C composite electrode
delivers high capacity and good capacity retention.
After 100 cycles, it still maintains a high capacity of
814 mA h g−1 without apparent capacity fading
during discharge-charge processes. As the amount Fig. 8 a Cyclic performance of MoO2-C composite electrode,
of added ammonium molybdate solution increases pure carbon coating prepared by carbonization of PAN and pure
MoO2 prepared by thermal decomposition of ammonium molyb-
from 0.6 to 1.2 g, although MoO2-C composite elec- date at a current density of 100 mA g−1. b Rate performance of
trode maintains its capacity well in processes of MoO2-C composite electrode at current densities of 100, 200, 500,
d i s c h a rg e - c h a rg e , i t s c a p a c i t y d e c e a s e s t o 1000, 2000, 5000, and 100 mA g−1
332 Page 8 of 11
Fig. 9 Nyquist plot of the MoO2-C composite electrode
current density for every 10 cycles from 100 to
5000 mA h g − 1 and then returning back to
100 mA h g−1 (Fig. 8b). The composite electrode
demonstrates outstanding high rate performance with
average capacities of 826, 809, 697, 568, 383, and
188 mA h g−1 at current densities of 100, 200, 500,
1000, 2000, and 5000 mA g−1. As the current den-
sity decreases from 5000 to 100 mA g−1, its average
capacity increases from 188 to 781 mA h g−1, which
indicates the electrode is highly stable and
reversible.
EIS of the MoO2-C composite electrode after 100 cy-
cles was measured. Its Nyquist plot, as presented in Fig. 9,
displays a semicircle in the high frequency region and an
inclined line in the low frequency region. The semicircle is
related to charge transfer resistance (Rct) and electrical
double layer capacitance (Cdl), and the inclined line is
Warburg impedance (Zw), indicating the lithium-ion
Table 1 Comparison of our work with reported MoO2-C composites
Materials Size of MoO2 (nm) Reversible capacity Current density Potential References
(mA h g−1)
MoO2@C hollow 200
micro-spheres
Carbon-coated 20 (width)
MoO2 nanobelts
Carbon-encapsulated 15.95
MoO2 nanoparticles
MoO2-loaded carbon 12
hollow spheres
Carbon-encapsulated MoO2 nanoparticles 5–10
J Nanopart Res (2017) 19: 332
diffusion in the bulk of electrode (Zhou et al. 2015a, b).
Obviously, the semicircle of the MoO2-C composite is
smaller than carbon-coated MoO2 nanoparticles with a
size of 20–50 nm dispersed in graphene aerogel (Zhou
et al., 2015a, b), MoO2 nanoparticles with a size up to tens
of nanometers grown on carbon fibers (Zhou et al. 2017),
and MoO2 nanoparticles with a size of 15 nm distributed
on ordered mesoporous carbon (Chen et al. 2013). The
estimated Rct values of the MoO2-C composite, carbon-
coated MoO2 nanoparticles/graphene aerogel (Zhou et al.
2015a, b), MoO2 nanoparticles/carbon fibers (Zhou et al.
2017), and MoO2 nanoparticles/ordered mesoporous car-
bon (Chen et al. 2013) are 18, 105, 95, and 85 Ω, respec-
tively. Additionally, the impedance slope of the MoO2-C
composite electrode is high, which indicates high mobility
of lithium ions in the composite electrode. The lower Rct
value and high mobility of lithium ions is attributed to
ultrafine size of the MoO2 nanoparticles.
Comparing with the electrochemical performance
of other published MoO2-C composites as presented
in Table 1 (Liu et al. 2014; Yang et al. 2012a, b; Liu
et al. 2016a, b; Gao et al. 2014), the copper-
supported MoO2-C composite synthesized in our
work delivers higher capacity. It also exhibits excel-
lent cyclic and rate performance. The high electro-
chemical performance of the composite can be at-
tributed to the following. Firstly, the ultrafine MoO2
nanoparticles can avoid their cracking and crum-
bling causing by lithium-ion insertion and extrac-
tion, and shorten lithium-ion diffusion distance; sec-
ondly, the carbon matrix can improve the electronic
conductivity of MoO2 and prevent ultrafine MoO2
nanoparticles from agglomeration; thirdly, the po-
rous structure of carbon can increase contact area
(mA g−1) range (V)
677.4 100 0–3 Liu et al. 2014
727 100 0–3 Yang et al. 2012a, b
656 450 0–3 Liu et al. 2016a, b
574 50 0–3 Gao et al. 2014
814 100 0–3 Our work
697 500
J Nanopart Res (2017) 19: 332
of electrode with electrolyte, shorten lithium-ion
diffusion distance, and provide space to buffer the
volume change of MoO2 during discharge-charge
processes; and fourthly, the copper-supported
MoO2-C composite as an integrated anode is free
of conductive agents and adhesives, and the tightly
bonding interface can maintain close contact be-
tween the composite and the copper foil during
discharge-charge processes.
Conclusion
Copper-supported MoO2-C composite was success-
fully synthesized through the knife coating stable
PAN-DMF-H2O system containing ammonium mo-
lybdate on the surface of copper foil, and subse-
quently sintering the formed copper-supported film
at 400 °C in a vacuum. The Stable PAN-DMF-H2O
system containing ammonium molybdate suitable
for knife coating technique can be prepared through
controlling amount of added ammonium molybdate
solution and slowly dropping the solution under
constant ultrasonic vibration. The obtained MoO2-
C composite with carbon content of 34 wt% is
comprised of ultrafine MoO2 nanoparticles and the
porous carbon matrix. The MoO2 nanoparticles have
monoclinic crystal structure and their size is 5–
10 nm. The porous carbon matrix has amorphous
structure and its pore size is concentrated at 1–3 nm.
The MoO2-C composite coating attaches tightly on
the surface of copper foil and no crack can be
observed at their interface. Being employed as the
integrated anode, the copper-supported MoO2 -C
composite delivers discharge capacity, charge capac-
ity, and coulombic efficiency of 1342 mA h g−1,
959 mA h g−1, and 71.44% respectively during the
initial cycle; demonstrates a high capacity of
814 mA h g−1 at a current density of 100 mA g−1
after 100 cycles and excellent capacity retention
performance in cyclic performance testing; and dis-
plays average capacities of 809, 697, 568, 383, and
188 mA h g−1 at current densities of 200, 500, 1000,
2000, and 5000 mA g−1 respectively in rate perfor-
mance testing. Its excellent battery performance is
related to its carbon-encapsulated ultrafine MoO2
nanoparticle structure, its porous structure, and inte-
grated anode with MoO2-C composite coating tight-
ly attaching on the surface of copper foil.
Page 9 of 11 332
Funding The funds of our work mainly came from Shanghai
Municipal Education Commission (High-energy Beam Intelligent
Processing and Green Manufacturing). We also appreciate Gradu-
ate Students Innovation Program of Shanghai University of Engi-
neering Science (16KY0512) for its financial support.
Compliance with ethical standards
Conflict of interest The authors declare that they have no con-
flict of interest.
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