J Mater Sci (2019) 54:4212–4224

Energy
E N E R G Y Mmaterials
ATERIALS

One-pot co-precipitation synthesis of Fe3O4

nanoparticles embedded in 3D carbonaceous matrix
as anode for lithium ion batteries
Qing Ai1 , Zewei Yuan3 , Renzhong Huang1 , Canxing Yang1 , Guodong Jiang1,2 , Jian Xiong1,2 ,
Zhen Huang1 , and Songdong Yuan1,2,*

1
Hubei Collaborative Innovation Center for High-Efficiency Utilization of Solar Energy, Hubei University of Technology,
Wuhan 430068, People’s Republic of China
2
The Synergistic Innovation Center of Catalysis Materials of Hubei Province, Wuhan 430068, People’s Republic of China
3
College of Chemistry, Nankai University, Tianjin 300071, People’s Republic of China

Received: 1 September 2018 ABSTRACT

Accepted: 12 November 2018
Published online:
21 November 2018
Ó Springer Science+Business
Media, LLC, part of Springer
Nature 2018
Fe3O4@C nanoparticles with a 3D net-like structure were synthesized via a facile
and scalable one-pot co-precipitation followed by a subsequent carbonization in
an Ar atmosphere. Verified by scanning and transmission electron microscopy
characterization, it can be seen that Fe3O4 nanoparticles with the size of
10–15 nm were embedded in a uniform carbon shell with a thickness of around
2 nm. Furthermore, the corresponding XRD and EDS analysis combined with
TEM images also proved that the thin carbon layer on the nano-scale Fe3O4 was
amorphous. The charge/discharge tests showed that Fe3O4@C composite
delivered an excellent reversible capacity of 980 mAh g-1 after 100 cycles at a
current density of 92.4 mA g-1, which was much higher than that of the pure
Fe3O4 (170 mAh g-1) synthesized by the same method. The outstanding
reversible capacity is attributed to the small size of Fe3O4 particles and the high
conductivity and mechanical strength of the amorphous carbon layer, which
accelerates the electron transfer and relieves structure collapse caused by
mechanical stress, thus maintaining a superior electrochemical stability.

Introduction more researchers are turning their attention to gra-

The commercialized graphite anode materials cannot
meet the requirement of heavy-duty electric vehicles
for high energy and power density lithium ion bat-
teries due to their limited theoretical specific capacity
(372 mAh g-1) and low energy density [1–3]. Thus,
phite alternative materials. Among them, silicon, tin
and transition metal oxides with higher theoretical
specific capacity, lower cost, high safety voltage,
having attracted widespread attention, are suit-
able for a new generation of alternative anode
material [2, 4–7]. Although silicon- and tin-based

Address correspondence to E-mail: yuansongdong@aliyun.com

https://doi.org/10.1007/s10853-018-3141-3
J Mater Sci (2019) 54:4212–4224
materials have a high theoretical lithium storage
capacity through the formation of Sn or Si alloy
compounds, a great volume expansion encountering
in the charge and discharge of the two metal-based
materials strongly restricts their application.
Among transition metal oxides, Fe3O4 has become
one of the most outstanding electrode materials
because of high theoretical specific capacity
(924 mAh g-1), natural abundance, high environ-
mental compatibility, low cost and toxicity [2, 4, 5].
Different from the lithium storage mechanism of tin-
or silicon-based materials [8, 9], Fe3O4 provides high
lithium storage capacity via the corresponding
chemical reaction (Fe3O4 ? 8Li? ? 8e- ? 4Li2-
O ? 3Fe). Nevertheless, the Fe3O4 also suffers from
the mechanical stress caused by the volume change
during the charge and discharge that leads to active
materials to pulverize and fall off from the current
collector, thus greatly reducing the reversible capac-
ity of the electrode material [10, 11]. Moreover, the
poor conductivity of Fe3O4 hampers the electron
transport in Fe3O4 particles, which results in severe
polarization during the cycle and then affects the
electrochemical reversibility and coulomb efficiency
[4]. In order to resolve the above problems and give
full play to the advantages of Fe3O4 as electrode
material, diverse nanostructures of Fe3O4 have been
designed to retard the severe volume expansion
effect in cycles as well as shorten the transmission
path of electrons and ions, such as nanoparticles
[1, 4, 12–16], nanowires [17–19], nanorods [20], hol-
low nanofibers. [21–25]. But it is worth noting that
nano-scale materials are prone to aggregate into bulk
particles, leading the fracture of particles and the
electrical contact loss between active material and
current collector. Therefore, a low reversible specific
capacity and pool cycling performance are observed.
Based on this situation, constructing core–shell
structures [12, 18, 20], nanoparticle composite struc-
tures, multi-stage heterostructures by combining
Fe3O4 with conductive materials possessing large
specific surface and high mechanical strength may be
a new outlet [22, 26–31]. Recent researches reveal that
embedding nanostructure Fe3O4 in carbon layer is an
effective method to greatly improve the cycle stability
and rate performance of Fe3O4 as lithium battery
electrode, delaying rapid capacity decay in the cycle
[14, 23]. For instance, Sathish [2] demonstrated
Fe3O4/GNS (W:W = 40:60) nanocomposite prepared
using hydrothermal method displayed very high
4213
reversible capacity of 675 mAh g-1 after 50 cycles.
The work reported by Zhao [13] showed that a facile
and scalable in situ synthesis strategy could be
developed to fabricate Fe3O4@C nanoparticles
homogeneously anchored on two-dimensional (2D)
porous graphitic carbon nanosheets (Fe3O4@C@PGC
nanosheets) as a durable high-rate anode material for
lithium ion battery, exhibiting only 3.47% capacity
loss (10 C) after 350 cycles. However, most of these
fabrication methods for carbon-coated Fe3O4 are
complicated [1, 14], and in general, several steps are
demanded. Lv et al. [1] firstly spent more than 100 h
fabricating Fe2O3 aerogel, and subsequently, anneal-
ing and CVD process were adopted to obtain Fe3O4/
C composite. Yu et al. [14] firstly prepared PS-COOH
latexes in N2 atmosphere for 24 h. Then, two inter-
mediates of PS@Fe3O4 and PS@Fe3O4@polydopamine
were acquired successively. Finally, Fe3O4/C com-
posite was collected by annealing PS@Fe3O4@poly-
dopamine under N2 flow. Chen et al. [23] also took
three complicated steps to synthesize Fe3O4/C com-
posite, in which a complex electrospinning technique
was required. Hydrothermal method is also widely
used to prepare Fe3O4. However, this method is time-
consuming, and high temperature and pressure are
required. To some extent, it goes against the ideas for
low energy consumption and large-scale application.
Herein, we successfully fabricated Fe3O4@phenolic
resin (Fe3O4@PF) by a one-pot co-precipitation
method, which had characteristics of simple opera-
tion, mild synthetic conditions, low operating costs
and mature preparation technology. Subsequently,
Fe3O4 nanoparticles embedded in a uniform carbon
layer (Fe3O4@C composite) could be obtained by
transferring Fe3O4@PF into a tube furnace heating at
500 °C for 2 h. The galvanostatic charge/discharge
tests indicated that, compared to the pure Fe3O4
nanoparticles, Fe3O4@carbon composites displayed a
significant cyclability, a specific capacity of
980 mAh g-1 being retained even after 100 cycles.
However, the capacity of pure Fe3O4 rapidly decayed
to 170 mAh g-1 within 30 cycles. The rate perfor-
mance tests showed that Fe3O4@C materials could
provide a discharge specific capacity of 960 mAh g-1,
850 mAh g-1, 650 mAh g-1, 370 mAh g-1,
-1
150 mAh g at the charge/discharge rates of 0.1 C,
0.2 C, 0.5 C, 1 C, 2 C, respectively, which were much
higher than that of pure Fe3O4. The results demon-
strated using our strategy, an excellent lithium stor-
age performance for Fe3O4@C composite could be
4214
readily obtained, which had a promising potential as
lithium ion battery anode.
Experimental
Materials
All reagents used were analytical grade without
further purification. Ferric chloride hexahy-
drate(FeCl3
6H2O, C 99%), ferrous sulfate heptahy-
drate (FeSO4
7H2O, 99–101%), ammonia (25–28%),
formaldehyde solution (37–40%) were purchased
from Sinopharm Group Chemical Reagent Co. Ltd.,
and phenol (99%) was provided by Tianjin Dongli
District Chemical Reagent Factory.
Preparation of Fe3O4@C
The ultrathin carbon shell-coated nano-sized Fe3O4
was prepared by one-pot co-precipitation followed
by annealing treatment. Experimental details were
briefly described as follow. Firstly, 6.08 g of FeCl3-
6H2O and 4.17 g of FeSO4
7H2O were dissolved in
30 ml of deionized water to form a clear yellow
solution and transferred to a flask under a vigorous
mechanical agitation, where aqueous ammonia solu-
tion was quickly added to adjust the pH to 10 and a
constant temperature of 50 °C was kept for 1 h.
Subsequently, 1.41 g of phenol and 3.36 ml
formaldehyde solution dissolved in 20 ml of deion-
ized water was introduced into the flask. Then, the
temperature was ramped to 90 °C and kept constant
for 7 h. After the reaction was finished, it was cooled
to room temperature and the precipitate was
repeatedly washed to neutrality with deionized
water. A dark brown of Fe3O4@PF composite could
be obtained after freeze-drying of the precipitate for
24 h. Finally, a certain amount of Fe3O4@PF com-
posite was transferred into a tube furnace and heated
at 500 °C for 2 h with a ramping rate of 5 °C min-1
under inert atmosphere. Accordingly, the products,
denoted as Fe3O4@C, were obtained.
Preparation of Fe3O4
The preparation process was the same as Fe3O4@C
except the addition of phenol and formaldehyde.
Typically, a certain mass ratio of FeSO4
7H2O and
FeCl3
6H2O were dissolved in deionized water to
J Mater Sci (2019) 54:4212–4224
form a precursor solution. After the addition of
ammonia to the above mixture at 50° for 1 h under a
vigorous mechanical agitation, the precipitate was
washed with deionized water to neutrality and
freeze-dried for 24 h. Hence, the black Fe3O4 powder
was obtained.
Characterization
The morphologies of the samples were characterized
by field emission scanning electron microscopy
(SEM, Japan Hitachi Model S4800) and high-resolu-
tion transmission electron microscopy (TEM, JEM-
2100F). The energy-dispersive spectrometer (EDS,
JEOL JEM-2100F), X-ray photoelectron spectroscopy
(XPS, Thermo ESCALAB 250XI) measurements were
utilized to determine the element types and propor-
tions in the samples. The graphitization degree and
content of carbon in the composites were analyzed by
Thermogravimetric (TG-DSC, TA) and Raman spec-
trometer (Raman, LabRam HR Evolution) with
532 nm at room temperature. Powder X-ray diffrac-
tion (XRD, PANalytical X’PertPro) was conducted to
analyze the crystalline phase of the samples. The test
conditions were as the following: Cu Ka
(k = 0.15405 nm), tube pressure 40 kV, tube current
40 mA, scan rate 5° min-1.
Electrochemical measurements
The active material, conductive carbon black and
PVDF were dispersed in N-methyl pyrrolidone in a
mass ratio of 8:1:1 to form a slurry and then uni-
formly coated on copper foil. After vacuum drying at
80 °C for 12 h, the copper foil was cut into circular
pieces of 12 mm in diameter. Then, active material-
coated copper foil as a working electrode, a lithium
metal electrode as a reference electrode, 1 M LiPF6 in
ethylene carbonate/dimethyl carbonate (V:V = 1:1)
as electrolyte, microporous polypropylene film (Cel-
gard 2400) as a separator were assembled to half cell
(CR2032) in a glove box filled with Ar (Mikrouna,
China, [O2] \ 1 ppm, [H2O] \ 1 ppm). The cell was
charged and discharged at room temperature by
using CT2001a battery tester (LAND Electronic Co.).
The potential window was in the range of 0.01–3.0 V.
Cyclic voltammograms (CV) was obtained on the
electrochemical workstation (Zennium, Zahner) with
a sweep rate of 0.1 mV s-1. The electrochemical
impedance spectroscopy (EIS) was conducted on an
J Mater Sci (2019) 54:4212–4224 4215

electrochemical workstation with a frequency range free water evaporated from room temperature to
of 0.01 Hz–100 kHz. 150 °C with a weight loss of 0.4% on the TG curves,
and the major weight loss (17.6%) happened at
150–400 °C. An obvious exothermic peak located at
Results and discussion 363 °C appeared in DSC curves, which was attributed
to the conversion of carbon to CO2/CO. Another
Morphology and structural characterization small exothermic peak between 580 and 640 °C was
of Fe3O4@C composites related to that phase transformation of maghemite
into hematite in air. Thus, the remaining phase was
Figure 1a shows XRD patterns of pure Fe3O4, Fe3- actually Fe2O3. The calculated weight fraction of
O4@PF and Fe3O4@C composites, respectively, whose
Fe3O4 and carbon was 79.3% and 20.7% in Fe3O4@C
crystal structures were characterized as below. The
composite according to TG-DSC analysis, respec-
diffraction peaks for the three sample were located at
tively [13, 34, 35].
the same positions, and all the patterns did not dis-
The element valence in as-prepared Fe3O4@C
play any other miscellaneous peaks, which could be
composite was characterized by X-ray photoelectron
indexed to magnetite Fe3O4 (JCPDS No. 19-0629)
spectroscopy (XPS), and the results are displayed in
[31–33]. Additionally, the diffraction intensity of
Fig. 2. A survey spectrum containing C 1s, O 1s, and
peaks for different samples was basically identical,
Fe 2p proved the presence of these three elements in
indicating that the phenolic resin in situ growing on
Fig. 2a. In the Fe 2p fine spectrum of Fe3O4@C com-
the surface of Fe3O4 did not change the crystallinity
posite, the Fe 2p region was deconvoluted into six
of Fe3O4. Furthermore, the crystallite size of Fe3O4
peaks, as shown in Fig. 2b. There were two spectral
nanoparticles in the Fe3O4@C composites was calcu-
bands located at 725.3 eV, 711.9 eV, which were
lated to be 38 nm at (311) diffraction peak by using
corresponded to 2p1/2, 2p3/2 of Fe3? species, respec-
Scherrer’s formula, which was almost the same size
tively. And the other two peaks at binding energy of
as the pure Fe3O4 nanoparticles (34 nm), suggesting
723.8 eV and 710.6 eV could be attributed to 2p1/2
post-carbonization in the preparation procedure of
and 2p3/2 of Fe2? species [18, 36]. The remaining two
Fe3O4@C did not affect the crystallite size of Fe3O4 weak peaks at 719 eV and 733 eV were satellite
core. Besides, no characteristic diffraction peaks peaks, indicating the purity and successful formation
belonging to carbon materials were observed, which of the Fe3O4 phase in the Fe3O4@C nanoparticles [36].
may be attributed to the relatively low content of
The high-resolution O 1s spectrum and C
carbon in composites. On the other hand, the carbon
1s (284.8 eV) spectrum are shown in Fig. 2c–d. The O
converted from thermal decomposition of phenolic
1s spectral band (Fig. 2d) consisted of three peaks
resin at a high temperature was in relatively poor
distributed at binding energy of 533.4 eV, 531.4 eV
crystallinity or amorphous, which was hardly detec-
and 530.3 eV, respectively, which were attributed to
ted by XRD [16]. In order to further illustrate the
oxygen anion (O2-) in Fe3O4, hydroxide (OH-) in the
carbon structure, Raman spectrometry was used for
surface of metal oxide and specifically physically
analyzing the graphitization degree. Two obvious
adsorbed H2O, respectively [37, 38].
characteristic peaks located at 1365 and 1590 cm-1
The morphology of pure Fe3O4 and Fe3O4@C was
are observed in Fig. 1b, which were corresponded to
demonstrated by SEM images, as shown in Fig. 3.
D and G bands of graphite, respectively [16, 22, 23].
With a low magnification, it was noted that pure
D-band indicating the disordered carbon was related
Fe3O4 preferred to agglomerate into larger blocks
to vibration of sp3 carbon atoms, while G-bond rep-
with various shapes and sizes. The largest block of
resenting ordered graphite carbon was associated
Fe3O4 aggregates had a lateral dimension of up to
with the vibration of sp2 carbon atom. Fortunately,
1 lm. When SEM image was further magnified, it
the presence of the carbon coating also could be was found that blocked Fe3O4 consisted of a plenty of
confirmed by the subsequent characterizations of TG, closely packed Fe3O4 nanoparticles with a much
XPS, TEM and EDS. smaller size of about 25 nm, as shown in the gray–
To measure the content of carbon and Fe3O4,
black region of Fig. 3c. Meanwhile, several larger
thermogravimetry/differential scanning calorimetry
Fe3O4 particles were found to mainly distribute on
(TG/DSC) was carried out, as shown in Fig. 1c. The
the edge of blocked Fe3O4 (as seen in the white region
4216 J Mater Sci (2019) 54:4212–4224

(a)

(311)
(b) 1590

(220)

(511)

(440)
1365

(400)
(111)

(222)

(422)
Intensity / a.u.

Fe3O4@C

Intensity/a.u.
Fe3O4@PF

Fe3O4

JCPDS:19-0629

10 20 30 40 50 60 70 80
800 1000 1200 1400 1600 1800 2000
2Theta/ degree
Raman Shift/cm-1

105
(c) 0.41% 3
Exo
100 0

-3

DSC(mW/mg)
TG(Wt.%)

95 o
609.1 DSC
-6
17.56% -9
90
-12
o
85 363.6 TG -15

-18
80
100 200 300 400 500 600 700 800 900
o
Temperature( C)

Figure 1 a XRD patterns of Fe3O4; Fe3O4@PF and Fe3O4@C composites, b Raman spectra of Fe3O4@C composites, c TG-DSC curves
of the Fe3O4@C composites.

of Fig. 3c). Yet, Fe3O4@C composite particles were cycling was observed, as shown in Fig. 3e–f. The
assembled into a flower-like morphology, which electrodes (before and after cycling) displayed uni-
could be clearly noted in Fig. 3b. The special mor- form and complete morphology, and no scattered
phology may be attributed to the fact that in situ fragments or obvious cracks appeared. It could be
polymerization of phenolic resin inhibited the con- seen that the overall structure of Fe3O4@C composite
tinued growth of Fe3O4 crystals and blocked the electrode after cycling for 100 cycles expanded a little
agglomeration of Fe3O4 particles, resulting in many volume compared with the electrode before cycling.
loose voids presented between particles and relieving High-magnification SEM image (Fig. 3g–h) illus-
large volume expansion effect as well as accelerating trated that the carbon coating layer still acted as a
the transport of the ions. According to the magnified linking matrix nearby Fe3O4 particles. The 3D net-like
SEM image in Fig. 3d, it could be seen that Fe3O4 structure of cycled electrode was basically not
nanoparticles were well packaged in gel-like carbon destroyed, which proved the outstanding cycling
layer, which acted as the conductive connection stability of Fe3O4@C composite electrode. The corre-
matrix for particles to shorten the transmission paths sponding EDS analysis (Fig. 3i) demonstrated that
of electrons and ions, and finally improved the the composite was mainly composed of Fe, O and C.
reversible capacity and rate performance of Fe3O4. In The elemental distribution (Table 1) in the composite
order to illustrate the high structural stability of the revealed that the C content was estimated to be
3D net-like Fe3O4@C composite, the fabricated Fe3- 18 wt%.
O4@C electrode before and after charge–discharge
J Mater Sci (2019) 54:4212–4224 4217

Figure 2 A survey XPS

(a) (b) Fe2p3/2
spectrum a of Fe3O4@C
Fe2p1/2 satellite peak
composites and fine XPS
spectra of b Fe 2p, c O 1s and Fe
3+

Intensity(a.u.)
2+
d C 1s. C1s O1s Fe

Intensity(a.u.)
Fe2p
3+
2+
Fe
Fe
satellite peak

200 300 400 500 600 700 710 720 730 740
Binding energy(eV) Binding energy(eV)

(c) O1s
(d) C1s
O2-

Intensity(a.u.)
Intensity(a.u.)

OH -
H 2O

530 535 540 545 276 280 284 288 292

Binding energy(eV) Binding energy(eV)

In order to intuitively validate the structure of 3D
net-like Fe3O4@C composites, TEM was adopted to
investigate the structure of Fe3O4@C composites. As
shown in Fig. 4a–e, nano-sized Fe3O4 (black particles)
uniformly distributed in the TEM image and all the
Fe3O4 particles possessed a narrow size distribution,
namely 10–15 nm in diameter. Fe3O4 nanoparticle
was tightly covered by a thin carbon layer in higher
magnification transmission images (Fig. 4c–d), lead-
ing to a special 3D net-like complex structure, in
which the carbon coating layer (marked by the white
arrow in Fig. 4d) acted as a linking matrix nearby
Fe3O4 particles to form conductive network, and
further to accelerate the electron transmission in the
active material. It was noted in the high-resolution
TEM image of Fe3O4@C (Fig. 4e) that the lattice
interplanar spacing of 0.302 nm, 0.251 nm was well
assigned to the (220), (311) lattice planes of Fe3O4,
respectively (as indicated by the white arrows),
which confirmed that the Fe3O4 synthesized had a
high degree of crystallinity, coinciding well with the
results of SAED diagram (Fig. 4f). Simultaneously, no
obvious lattice fringes but a turbostratic structure
was observed in the carbon layer in Fig. 4e, whose
thickness was around 2 nm, confirming that carbon
layer was amorphous. This result was consistent with
the above EDS spectra and XRD analysis.
Electrochemical performance
In order to investigate electrochemical performance
of Fe3O4@C as anode material for lithium battery, the
cycle performance tests of Fe3O4@C composites and
Fe3O4 were carried out at current densities of 0.1 C.
As shown in Fig. 5, the Fe3O4@C composite retained
a high reversible specific capacity of 980 mAh g-1
after 100 cycles, which was 82% of the initial dis-
charge specific capacity. It was worth noting that the
coulomb efficiency of Fe3O4@C composite electrode
was only 76% in the first cycle, but exceeded 95% in
the following cycles, which suggested the promising
application in electrode material. However, for the
pure Fe3O4 lacking the protection of carbon layer, the
capacity rapidly decayed to 170 mAh g-1, which was
less than 13% of the first capacity, after 100 cycles at
the same current density. This was due to the great
mechanical strain deriving from reuniting of particles
during the cycle. The excellent cycle stability for
4218 J Mater Sci (2019) 54:4212–4224

Fe3O4@C composite, certified by above results, was

mainly attributed to the 3D net-like structure of Fe3-
O4@C material. In the fabrication process of Fe3O4@C,
co-precipitation method assisted with the ultrasoni-
cation was firstly applied to synthesize Fe3O4 parti-
cles with a uniform size of around 10 nm. Then nano-
sized Fe3O4 was viewed as the nucleation and growth
sites for the subsequent phenol and formaldehyde
in situ polymerization, which could enable the nano-
sized Fe3O4 to be uniformly covered by phenolic
resin. During the carbonization, phenolic resin was
converted to carbon and coated on the surface of
Fe3O4, which would retard the agglomeration of
Fe3O4 nanoparticles. Thus, the nano-scale feature of
Fe3O4 particles in this composite was kept to be able
to relieve volume effect during charge/discharge
cycles. In addition, the carbon layer not only con-
structed a conductive network between Fe3O4 parti-
cles to enhance the electron transmission of the whole
material but also acted as buffer layer to abate the
expansion/contract of Fe3O4, and further maintained
structural stability and high reversible capacity.
Cyclic voltammetry of Fe3O4@C composite was
performed with a voltage window of 0.01–3 V and a
sweeping rate of 0.1 mV s-1, and the corresponding
CV curves are shown in Fig. 6. In the first cycle, a
weak reduction peak and an intense reduction peak
appeared at 0.8 V and 0.55 V, respectively, corre-
sponding to the insertion of Li? to Fe3O4 (Fe3O4-
? x Li? ? x e- ? LixFe3O4) and the reduction
reaction of Fe3? and Fe2? to Fe0, which was accom-
panied by the formation of SEI film on the surface of
the electrode material [1, 13, 23]. In the subsequent
(i) Fe
cycles, the reduction peak shifted to a higher poten-
tial, which is mainly ascribed to the electrode polar-
ization in the first cycle process [24, 32, 39].
Intensity / a.u.

O Meanwhile, the peak current intensity became obvi-

ously weaker, indicative of an irreversible reaction in
Fe Cu the first cycle, which consumed a large amount of
lithium ions. A broad oxidation peak appearing at
C 1.6 V–1.9 V could be assigned to the oxidation reac-
Fe
tion of Fe0 to Fe2? and Fe3? during the first charging
Cu Cu process [23, 32, 39], which was consistent well with
the results of previous report. We also found that the
0 2 4 6 8 10 CV curves of the subsequent two cycles almost
Energy/ KeV overlapped, revealing that the electrode material had
a high electrochemical reaction reversibility.
Figure 3 SEM images of a, c Fe3O4, b, d Fe3O4@C composite
samples, and Fe3O4@C electrodes before (e, g) and after (f, To further investigate electrode lithium storage
h) 100 cycles. i EDS pattern of Fe3O4@C composites. performance, the charge–discharge curves of Fe3-
O4@C and Fe3O4 for the 1st, 2nd, 10th, and 50th cycle
J Mater Sci (2019) 54:4212–4224
Figure 4 a–c TEM images
and d, e high-resolution TEM
of Fe3O4@C composites;
f SAED diagram of Fe3O4@C
composites.
were gained at a current density of 92.4 mA g-1, as
displayed in Fig. 7. A obvious discharge platform at
0.8 V appeared during the first discharge cycle,
which was related to the generation of LixFe3O4
[40, 41]. The first charge–discharge profiles showed
that the charge and discharge capacities of the Fe3-
O4@C composite material were 1183 mAh g-1,
954.9 mAh g-1 along with a high coulomb efficiency
of 80.7%. Almost more than 96% in the subsequent
cycles was achieved. It was noteworthy that the
shape of charge–discharge curves for Fe3O4@C for
4219
the 10th and 50th cycle was almost the same as that of
the second cycle, and the discharge specific capacity
980 mAh g-1 was still maintained even in the 100th
cycle, which fully illustrated that Fe3O4@C synthe-
sized by in situ co-precipitation had excellent elec-
trochemical reversibility. While the reversible
capacity decay of pure Fe3O4 from the 10th to the
100th was very fast, suggesting an extremely poor
cycle stability. This was mainly attributed to the fact
that the mechanical stress resulting from embed-
ding/extraction of Li? in the Fe3O4 particles caused
4220
Figure 5 Cycle performance of Fe3O4@C composites and Fe3O4
at 0.1C rate.
Figure 6 CV curves of Fe3O4@C composites.
the material to pulverize and fall off from the current
collector, leading to a lower loading and poor electric
contact of active material, which remarkably affected
the cycling stability of the battery [42–44].
The rate capability of Fe3O4@C composites and
pure Fe3O4 nanoparticles was further evaluated, as
shown in Fig. 8. It was noteworthy that, for pure
Fe3O4 nanoparticles, an inferior rate performance
could be seen. The capacity was decreased during the
first several cycles at 0.1 C. As the discharge rate
raised to 0.5 C, the discharge capacity did not exceed
100 mAh g-1. In particular, at a high rate (2 C),
nearly no capacity could be gained. When the rate
was recovered to 0.1 C, a very low capacity of
250 mAh g-1 was delivered. However, Fe3O4@C
composites delivered a relatively high specific
capacity of 960 mAh g-1, 850 mAh g-1,
J Mater Sci (2019) 54:4212–4224
(a)
(b)
Figure 7 Charge and discharge profiles of a Fe3O4@C and
b Fe3O4 at 0.1 C rate.
650 mAh g-1 at 0.1 C, 0.2 C, 0.5 C, respectively. When
the discharge rate was increased to 1 C and 2 C, the
decline in the capacity became notable, namely
370 mAh g-1 and 150 mAh g-1 were retained. This
might be due to the sluggish reaction kinetic in Fe3-
O4@C. Additionally, the specific capacity of Fe3O4@C
was restored to 690 mAh g-1 after returning to 0.1 C,
indicating that a satisfactory performance was
obtained. Electrochemical performance and synthe-
sized method of Fe3O4@C electrode in the studies are
compared in Table 2. Remarkably, the Fe3O4@C
composite in this study delivered as high reversible
capacity and capacity retention as Fe3O4 composite
fabricated in other paper, however, the route applied
in the work had characteristics of simple operation,
J Mater Sci (2019) 54:4212–4224 4221

In order to illustrate the important role of the car-

bon coating on the electrochemical performance of
Fe3O4@C electrode materials, electrochemical impe-
dance spectroscopy was carried out with a frequency
range of 0.01 Hz to 100 kHz. The Nyquist spectra for
Fe3O4@C and Fe3O4 were presented in Fig. 9. The
curves were fitted according to the equivalent circuit
displayed in the inset of Fig. 9. The fitted results are
listed in Table 3. The shape of the curves for the two
electrode materials was basically similar, consisting
of a small semicircle appearing in the middle- and
high-frequency region and an oblique line existing in
the low-frequency area. The charge-transfer impe-
dance of Fe3O4@C (Rct = 114.7 X, represented by the
red line) extracted from fitting data using was sig-
Figure 8 Rate performance of Fe3O4@C composite and Fe3O4. nificantly smaller than that of pure Fe3O4 (Rct-
= 179 X, expressed by blue line). It was indicated
Table 1 The elemental content in the Fe3O4@C composites that Fe3O4@C had a faster electron transfer rate, being
beneficial for the improvement of rate performance of
Element Weight % K-factor
the electrode. This was mainly due to a high con-
C(k) 18.14 3.94 ductivity of carbon layer. As demonstrated in previ-
O(k) 24.67 1.947 ous papers, the oblique line appearing in the low-
Fe(k) 57.18 1.403 frequency region was associated with the diffusion of
ions in the electrode materials [13, 40], which was an
indication of the Warburg impedance. In general,
compared with pure Fe3O4, the electrochemical per-
mild synthetic conditions, low operating costs and formance of Fe3O4@C composite was remarkably
was more available to large-scale application. improved and it was more suitable as the anode for
the lithium ion battery.

Table 2 Comparison of electrochemical properties of electrode materials reported in the literature and this work

Materials Synthesized method Reversible capacity Current density Capacity References

(mAh g-1) retention (%)

Fe3O4/C Sol–gel route and CVD process 850/60 Cycles 100 mA g-1(0.11C) 70.8 [1]
Fe3O4@C Hydrothermal process and annealing 806/100 Cycles 100 mA g-1(0.11 66.3 [4]
nanoparticles C)
Fe3O4@C@PGC In situ synthesis and annealing 998/100 Cycle 924 mA g-1 (1 C) 97.7 [13]
nanoparticles
GN@C/Fe3O4 In situ electrospinning and annealing 872/100 Cycle 100 mA g-1(0.11 64.6 [20]
nanofibers C)
Fe3O4@C One-pot R-CHM strategy 505/100 Cycles 100 mA g-1(0.11 38.9 [22]
C)
G@Fe3O4@C In situ hydrolysis, polymerization 920/100 Cycles 200 mA g-1(0.22 65.7 [24]
and annealing C)
Fe3O4@C One-pot co-precipitation, 980/100 Cycle 92.4 mA g-1(0.1 82 This work
polymerization and annealing C)
640/40 Cycle 184.8 mA g-1(0.2 53.6 This work
C)
4222 J Mater Sci (2019) 54:4212–4224

electron and relieving volume effect. On the other

hand, the thin carbon matrix enhanced the electrical
conductivity of the composite material and served as
a buffer layer for Fe3O4 to accommodate volume
change and avoided Fe3O4 merging during cycle. The
method was simple in operation, mature in industrial
technology. Therefore, compared with other approa-
ches, it was suitable for large-scale production.

Figure 9 EIS spectra of Fe3O4@C composites and Fe3O4 in the
frequency range from 0.01 Hz to 100 kHz. The inset was a
corresponding equivalent circuit.
Table 3 Kinetic parameters of Fe3O4@C and Fe3O4 electrodes
Acknowledgements
This work is supported by the Open Fund of efficient
Utilization of Solar Energy by Hubei Province Col-
laborative Innovation Center [HBSKFZD2015001],
Cooperation projects of China-UK Research and
Innovation Bridge Project [2016YFE0124300] and
Maker Venture Funding Technology Innovation
(2007) [CKCY2017042814264604].

Samples Fe3O4@C Fe3O4

References
Rs (X) 2.8 2.0
Rct (X) 114.75 179 [1] Lv P, Zhao H, Zeng Z, Wang J, Zhang T, Li X (2014) Facile
CPE1-T 2.7E-05 1.9E-05 preparation and electrochemical properties of carbon coated
CPE2-P 0.78 0.76 Fe3O4 as anode material for lithium-ion batteries. J Power
W–R 658.5 287.8 Sources 259:92–97
W–T 11.9 5.4 [2] Sathish M, Tomai T, Honma I (2012) Graphene anchored
W–P 0.5 0.7 with Fe3O4 nanoparticles as anode for enhanced Li-ion
storage. J Power Sources 217:85–91
[3] Tian Q, Tian Y, Zhang Z, Yang L, Hirano SI (2014) Facile
synthesis of ultrasmall tin oxide nanoparticles embedded in
Conclusion carbon as high-performance anode for lithium-ion batteries.
J Power Sources 269:479–485
In summary, a co-precipitation method, featuring as [4] Zhang Y, Li Y, Li H, Zhao Y, Yin F, Bakenovd Z (2016)
simple operation, mild conditions and scalable Electrochemical performance of carbon-encapsulated Fe3O4
preparation, was used to prepare Fe3O4@PF, fol- nanoparticles in lithium-ion batteries: morphology and par-
lowed by an annealing treatment to obtain Fe3O4@C ticle size effects. Electrochim Acta 216:475–483
composites, in which Fe3O4 NPs (* 10 nm) were [5] Wang Y, Zhang L, Gao X, Mao L, Hu Y, Lou X (2014) One-
embedded in thin carbon layer. As an anode material, pot magnetic field induced formation of Fe3O4/C composite
when Fe3O4@C composites were assembled into a microrods with enhanced lithium storage capability. Small
half cell, compared with pure Fe3O4 electrode, the 10:2815–2819
Fe3O4@C composites exhibited more excellent cycle [6] Guo X, Fang X, Sun Y, Shen L, Wang Z, Chen L (2013)
stability (980 mAh g-1 after 100 cycles at 0.1 C) and Lithium storage in carbon-coated SnO2 by conversion reac-
rate performance (960 mAh g-1, 850 mAh g-1, tion. J Power Sources 226:75–81
650 mAh g-1, 370 mAh g-1, 150 mAh g-1 at 0.1 C, 0.2 [7] Wang C, Zhou Y, Ge M, Xu X, Zhang Z (2010) Large-scale
C, 0.5 C, 1 C, 2 C, respectively). While the capacity of synthesis of SnO2 nanosheets with high lithium storage
pure Fe3O4 rapidly decayed to 170 mAh g-1 after 30 capacity. J Am Chem Soc 132:46–47
cycles in the same current density. The superior [8] Liu H, Guo Z, Wang J, Konstantinov K (2010) Si-based
performance of Fe3O4@C was attributed to ultrafine anode materials for lithium rechargeable batteries. J Mater
Fe3O4 NPs shortening transfer pathway of Li? and Chem 20:10055–10057
J Mater Sci (2019) 54:4212–4224
[9] Hassoun J, Derrien G, Panero S, Scrosati B (2010) A
nanostructured Sn–C composite lithium battery electrode
with unique stability and high electrochemical performance.
Adv Mater 20:3169–3175
[10] Cabana J, Monconduit L, Larcher D, Palacı́n MR (2010)
Beyond intercalation-based Li-ion batteries: the state of the
art and challenges of electrode materials reacting through
conversion reactions. Adv Mater 22:E170–E192
[11] Martha S, Nanda J, Zhou H, Idrobo JC, Dudney NJ, Pannala
S, Dai S, Wang J, Braun PV (2014) Electrode architectures
for high capacity multivalent conversion compounds: iron (II
and III) fluoride. RSC Adv 4:6730–6737
[12] Zhang W, Wu X, Hu J, Guo Y, Wan Y (2008) Carbon coated
Fe3O4 nanospindles as a superior anode material for lithium-
ion batteries. Adv Func Mater 18:3941–3946
[13] He C, Wu S, Zhao N, Shi C, Liu E, Li J (2013) Carbon-
encapsulated Fe3O4 nanoparticles as a high-rate lithium ion
battery anode material. ACS Nano 7:4459–4469
[14] Liu L, Zhang H, Liu S, Chen S (2016) Hollow carbon
nanosphere embedded with ultrafine Fe3O4 nanoparticles as
high performance Li-ion battery anode. Electrochim Acta
219:356–362
[15] Li M, Du H, Kuai L, Huang K, Xia Y, Geng B (2017)
Scalable dry production process of a superior 3D net-like
carbon-based iron oxide anode material for lithium ion bat-
teries. Angew Chem 56:12649–12653
[16] Yu Y, Wang W, Jing Z, Zheng X, Geng X, Li J (2016) Three-
dimensional Fe3O4/carbonaceous matrix with long-life per-
formance for high-rate lithium ion batteries. J Alloy Compd
688:605–610
[17] Muraliganth T, Murugan AV, Manthiram A (2009) Facile
synthesis of carbon-decorated single-crystalline Fe3O4
nanowires and their application as high performance anode
in lithium ion batteries. Cheminform 41:7360–7362
[18] An Q, Lv F, Liu Q, Han C, Zhao K, Sheng J, Wei Q, Yan M,
Mai L (2014) Amorphous vanadium oxide matrixes sup-
porting hierarchical porous Fe3O4/graphene nanowires as a
high-rate lithium storage anode. Nano Lett 14:6250–6256
[19] Ma J, Wang K, Zhan MS (2015) Growth mechanism, elec-
trical and magnetic properties of Ag–Fe3O4 core–shell
nanowires. ACS Appl Mater Interfaces 7:16027–16039
[20] Guo J, Zhu H, Sun Y, Zhang X (2015) Construction of
sandwiched graphene paper@Fe3O4 nanorod array@-
graphene for large and fast lithium storage with an extended
lifespan. J Mater Chem A 3:19384–19392
[21] Chen Z, Zhou J, Wang X, Liao X, Huang X, Shi B (2016)
Natural collagen fiber-enabled facile synthesis of car-
bon@Fe3O4 core-shell nanofiber bundles and their applica-
tion as ultrahigh rate anode materials of Li-ion batteries.
RSC Adv 6:10824–10830
4223
[22] He J, Zhao S, Lian Y, Cui S, Zhou M, Wang L, Ding B
(2017) Graphene-doped carbon/Fe3O4 porous nanofibers
with hierarchical band construction as high-performance
anodes for lithium-ion batteries. Electrochim Acta
229:306–315
[23] Wu Q, Zhao R, Zhang X, Li W, Xu R, Diao G, Chen M
(2017) Synthesis of flexible Fe3O4/C nanofibers with
buffering volume expansion performance and their applica-
tion in lithium-ion batteries. J Power Sources 359:7–16
[24] Liu M, Jin H, Uchaker E, Xie Z, Wang Y, Gao G, Hou S, Li J
(2017) One-pot synthesis of in situ carbon-coated Fe3O4 as a
long-life lithium-ion battery anode. Nanotechnology
28:155603–155612
[25] Ma F, Hu H, Wu H, Xu C, Xu Z, Zhen L, Xiong W (2015)
Formation of uniform Fe3O4 hollow spheres organized by
ultrathin nanosheets and their excellent Lithium storage
properties. Adv Mater 27:4097–4101
[26] Wei D, Liu Y, Wang Y, Zhang H, Huang L, Yu G (2009)
Synthesis of N-doped graphene by chemical vapor deposi-
tion and its electrical properties. Nano Lett 9:1752–1758
[27] Su Y, Li S, Wu D, Zhang F, Liang H, Gao P, Cheng C, Feng
X (2012) Two-dimensional carbon-coated graphene/metal
oxide hybrids for enhanced lithium storage. ACS Nano
6:8349–8356
[28] Huang M, Chen C, Wu S, Tian X (2017) Remarkable high-
temperature Li-storage performance of few-layer Graphene-
anchored Fe3O4 nanocomposites as anode. J Mater Chem A
5:23035–23042
[29] Zhao X, Li X, Zhang S, Long J, Huang Y, Wang R (2017) A
three-dimensional sponge of graphene nanoribbons cross-
linked by Fe3O4 nanoparticles for Li? storage. J Mater Chem
A 5:23592–23599
[30] Liu J, Xu X, Hu R, Yang L, Zhu M (2016) Uniform hier-
archical Fe3O4@Polypyrrole nanocages for superior Lithium
ion battery anodes. Adv Energy Mater 6:1600256
[31] Chen J, Zhang Y, Lou X (2011) One-Pot synthesis of uni-
form Fe3O4 nanospheres with carbon matrix support for
improved Lithium storage capabilities. ACS Appl Mater
Interfaces 3:3276–3279
[32] Wang J, Zhong C, Wexler D, Idris N, Zhao X, Li Q, Hua K
(2011) Graphene-encapsulated Fe3O4 nanoparticles with 3D
laminated structure as superior anode in lithium ion batteries.
Chem Eur J 17:661–667
[33] Li J, Tan L, Wang G, Yang M (2015) Synthesis of double-
shelled sea urchin-like yolk-shell Fe3O4/TiO2/Au micro-
spheres and their catalytic applications. Nanotechnology
26:095601
[34] Daou TJ, Pourroy G, Bégin-Colin S, Grenche J, Ulhaq-
Bouillet C, Legaré P, Bernhardt P, Leuvrey C, Rogez G
4224
(2008) Hydrothermal synthesis of monodisperse magnetite
nanoparticles. Chem Mater 18:4399–4404
[35] Li K, Zhao Y, Janik MJ, Song C, Guo X (2016) Facile
preparation of magnetic mesoporous Fe3O4/C/Cu compos-
ites as high performance Fenton-like catalysts. Appl Surf Sci
396:1383–1392
[36] Nene AG, Takahashi M, Somani PR (2016) Fe3O4 and Fe
nanoparticles by chemical reduction of Fe(acac)3 by ascorbic
acid: role of water. World J Nano Sci Eng 6:20–28
[37] Tan C, Gao N, Deng Y, Deng J, Li J, Xin X, Zhou S (2014)
Radical induced degradation of acetaminophen with Fe3O4
magnetic nanoparticles as heterogeneous activator of per-
oxymonosulfate. J Hazard Mater 276:452–460
[38] Bhargava G, Gouzman I, Chun CM, Ramanarayanan TA,
Bernasek SL (2007) Characterization of the ‘‘native’’ surface
thin film on pure polycrystalline iron: a high resolution XPS
and TEM study. Appl Surf Sci 253:4322–4329
[39] Li W, Wu J, Chen Y, Wang X, Zhou R, Chen S, Guo Q, Hou
H, Song Y (2015) Hollow nitrogen-doped Fe3O4/carbon
nanocages with hierarchical porosities as anode materials for
lithium-ion batteries. Electrochim Acta 186:50–57
J Mater Sci (2019) 54:4212–4224
[40] Mitra S, Poizot P, Finke A, Tarascon JM (2010) Growth and
electrochemical characterization versus lithium of Fe3O4
electrodes made by electrodeposition. Adv Func Mater
16:2281–2287
[41] Taberna PL, Mitra S, Poizot P, Simon P, Tarascon JM (2006)
High rate capabilities Fe3O4-based Cu nano-architectured
electrodes for lithium-ion battery applications. Nat Mater
5:567–573
[42] Han S, Wang X, Huang Y, Tang Y, Ai Y, Jiang J, Wu D
(2015) Carbon encapsulated Fe3O4/graphene framework
with oriented macropores for Lithium Ion battery anode with
enhanced cycling stability. RSC Adv 5:98399–98403
[43] Liu Y, Duan Z, Xie X, Ye X, Zhu X (2016) h-BN nanosheets
as 2D substrates to load 0D Fe3O4 nanoparticles: a novel
hybrid anode material for lithium-ion batteries. Chem Asian
J 11:828–833
[44] Yi X, He W, Zhang X, Yue Y, Yang G (2017) Graphene-like
carbon sheet/Fe3O4 nanocomposites derived from soda
papermaking black liquor for high performance lithium ion
batteries. Electrochim Acta 232:550–560