Electrochimica Acta 186 (2015) 50–57

Contents lists available at ScienceDirect

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

Hollow Nitrogen-doped Fe3O4/Carbon Nanocages with Hierarchical

Porosities as Anode Materials for Lithium-ion Batteries
Li Wang, Jiafeng Wu, Yaqin Chen, Xiaohong Wang, Rihui Zhou, Shouhui Chen,
Qiaohui Guo, Haoqing Hou, Yonghai Song*
Key Laboratory of Functional Small Organic Molecule, Ministry of Education, Key Laboratory of Chemical Biology, Jiangxi Province, College of Chemistry and
Chemical Engineering, Jiangxi Normal University, Nanchang 330022, China

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

Article history: Hollow nitrogen (N)-doped Fe3O4/carbon (C) nanocages with hierarchical porosities have been
Received 3 August 2015 successfully synthesized by carbonizing polydopamine (PDA)-coated Prussian blue (PB). Scanning
Received in revised form 1 October 2015 electron microscopy, transmission electron microscopy, X-ray powder diffraction, X-ray photoelectron
Accepted 23 October 2015
spectroscopy and N2 adsorption/desorption isotherms were employed to characterize the hollow
Available online 29 October 2015
N-doped Fe3O4/C superstructures. Owing to their well-defined hierarchical porous structure and high
electric conductivity originated from N-doped carbon matrix, the unique hollow nanocages as anode
Keywords:
materials for Lithium ion batteries (LIBs) exhibited a specific capacity of 878.7 mA h g
1 after 200 cycles
Hierarchical porosity
Fe3O4
at the specific current of 200 mA g
1, which is much better than that of N-doped Fe3O4/C derived from
N-doped carbon pure PB (merely 547 mA h g
1). The novel construction with hollow interior nanoarchitecture,
Anode hierarchical porosity, high electrical conductivity, N-doped carbon, and the Fe3O4 nanoparticles
Lithium ion batteries incorporated into porous interconnected carbon framework make the special nanocomposites be very
promising Fe3O4-based anode materials.
ã 2015 Elsevier Ltd. All rights reserved.

1. Introduction strong elastic carbon framework could buffer the volume

variation of TMO during circulating period (which is a common
Lithium ion batteries (LIBs) have attracted tremendous atten- problem in TMO electrodes) [20–22]. Accordingly, various
tion owing to their widespread application, such as smartphone, synthetic methods were proposed to prepare high-performance
smart watches, notebook computer, other portable electronic TMOC for LIBs. For instance, diverse carbon-based materials were
equipments and so on [1–6]. Nevertheless, the current commercial used as supporting to anchor or encapsulate TMO nanoparticles
anode materials, graphite, limited the further application of LIBs (e.g., carbon nanotubes (CNTs)/TMO [18,23], graphene oxide
due to its poor theoretical capacity (only 372 mA h g
1) and inferior (GO)/TMO [12,14,16,24,25] and porous carbon (PC)/TMO [21,26]).
rate performance at lager specific current [2,4,7]. As the electronics In these works, the synthetic procedures of TMOC were tedious
consumption age is rapidly coming, higher demands on the battery and complicated. Thus the design of novel TMOC is still highly
performance for various electronic devices are becoming intensive. challenging.
As a result, study on developing new anode materials with high Metal organic frameworks (MOFs) with unique porosities and
performance is urgently required [8–10]. desirable versatile functionalities have been extensively used in
Among multitudinous new anode materials, transition metal various fields, including gas catalysis and separation, sensing,
oxides (TMO)/carbon (C) nanocomposites (TMOC) were very energy storage and so on [27–31]. As one kind of MOFs, Prussian
promising and potential anode materials (e.g., Fe3O4/C [11,12], blue (PB) was used as precursor to prepare TMOC for LIBs.
MnO2/C [13], Co3O4/C [14–19], etc). TMOC with multi-composi- However, the specific capacity of TMOC as anode materials
tions and various nanostructures have been investigated exten- decreased rapidly to 547 mA h g
1, indicating a coating process
sively due to the increased theoretical lithium storage, excellent was necessary to improve its performance. Herein, the PB@poly-
electrical conductivity and superior cyclability. What’s more, the dopamine (PDA) was developed as TMOC precursor via pH-
induced polymerization of dopamine on PB in this work. The
synthesis procedures and experiment condition were mild and
feasible thus possible for mass production. Then the PB@PDA
* Corresponding author. Tel./fax: +86 791 88120862.
E-mail address: yhsonggroup@hotmail.com (Y. Song). precursor were thermal treated to achieve hierarchical porous

http://dx.doi.org/10.1016/j.electacta.2015.10.134
0013-4686/ ã 2015 Elsevier Ltd. All rights reserved.
 L. Wang et al. / Electrochimica Acta 186 (2015) 50–57 51

hollow nitrogen (N)-doped Fe3O4/C (HPHNF) nanocages. As 2.4. Characterization

compared with the reversible capacity of 547 mA h g
1 of N-doped
Fe3O4/C originated from pure PB, the HPHNF could deliver a good X-ray powder diffraction (XRD) data were collected on a D/Max
capacity of 878.7 mA h g
1 at a specific current of 200 mA g
1 even 2500 V/PC X-ray powder diffractometer using Cu Ka radiation
after 200 cycles due to the N-doped carbon network possess (l = 1.54056 Å, 40 kV, 200 mA). Scanning electron microscopy
improved electrical conductivity and novel interior hierarchical (SEM) analysis was acquired on a HITACHI S3400 operated at an
porous hollow structure which are able to relieve the volume acceleration voltage of 20 kV equipped with a Phoenix energy
change during the discharge/charge processes and enhance the dispersive X-ray analyzer (EDXA). X-ray photoelectron spectros-
transfer of Li+. copy (XPS) was performed using an ESCA-LAB-MKII spectrometer
(VG Co., United Kingdom) with AlKa X-ray radiation as the source
2. Experiment for excitation. N2 adsorption/desorption isotherms were measured
at 77 K in a liquid nitrogen atmosphere using a Tristar 3000 volu-
2.1. Reagents and chemicals metric adsorption analyzer (Micromeritics Instrument Corpora-
tion, USA) after the samples were pretreated at 200  C for 12 h
Polyvineypirrolydone (PVP), K3[Fe(CN)6], graphite and HCl were under vacuum. Transmission electron microscopy (TEM) images
obtained from Sinopharm Chemical Reagent (Shanghai, China). were acquired on JEOL JEM-2100 microscopes operated at an
Dopamine hydrochloride (DAH) was obtained from Sigma-Aldrich. acceleration voltage of 200 KV.
Other reagents were purchased from Beijing Chemical Reagent
Factory (Beijing, China). Polyvinylidene fluoride (PVDF, Lefu 2.5. Electrochemical measurements
Shanghai Chemicals), carbon black (Kaisai Shanghai Chemicals),
copper foil (10 mm thickness, Jiayuan Guangzhou Company) and The working electrodes were made by a slurry coating
metallic Li foil (0.6 mm thickness, 99.9%, Zhongneng Tianjin procedure. The as-prepared samples were mixed with acetylene
Company) were used without further treatment. Other chemicals black and carboxymethyl cellulose in a weight ratio of 8:1:1 in N-
used in this study are analytical grade. All solutions were prepared methyl pyrrolidinone to form homogeneous slurry and then spread
with ultrapure water, purified by a Millipore-Q System (18.2 MV uniformly on copper foil which was acted as a current collector.
cm). The active material loading on copper foil was approximately
0.8 mg cm
2. The fabricated working electrodes were dried in a
2.2. Preparation of PB vacuum oven at 60  C for overnight. A celgard 2300 microporous
polypropylene film was used as the separator. The cells were
In a typical synthesis, PVP (3 g) and K3[Fe(CN)6] (113.3 mg) were assembled in an argon-filled glove box using Li foil as counter
successively dissolved in HCl solution (0.01 M, 40 mL) under electrodes. The electrolyte was made of 1.0 M LiPF6 dissolved in the
magnetic stirring to obtain a clear solution. The beaker was placed mixture of ethylene carbonate, diethyl carbonate and dimethyl
into an electric oven and heated at 80  C for 20 h. After aging, the carbonate (1: 1: 1 in volume). Cyclic voltammograms (CVs) was
precipitates were collected by centrifugation and washed in carried out with a CHI 760D electrochemical workstation (CH
ultrapure water and absolute ethanol for several times. After Instruments, Shanghai, China) using a conventional three-elec-
drying in a vacuum oven at 60  C for 12 h, PB crystals with around trode system with Li metal as the counter and reference electrode,
150-200 nm were obtained. active materials as the working electrode. Other electrochemical
experiments were carried out in a two-electrode coin cells. The
2.3. Synthesis of HPHNF nanocages nanocomposites electrochemical discharge/charge tests of the samples were
performed on a Neware BTS test system (Shenzhen, China) at
In a typical procedure, 400 mg PB and 400 mg DAH was added voltage limits of 3.00.01 V versus Li/Li+.
into 100 mL Tris-HCl (10 mM pH=8.5). Then the mixture was
sonicated for 30 min. After that, the mixture was stirred for 24 h at 3. Results and discussion
room temperature. Then, the product was centrifuged and
washed with ethanol and water to obtain the PB@PDA nano- PB nanocubes were firstly prepared as the raw material to
composites. Finally, the PB@PDA nanocomposites were calcined synthesize PB@PDA through a simple strategy. The PB nanocubes
at 550  C with a heating rate of 10  C min
1 and held for 1 h under with smooth surface and mean size of 150-250 nm are observed
N2. The HPHNF nanocomposites were then obtained. The clearly in the SEM image as shown in Fig. 1a, indicating the
preparation procedure was illustrated in Scheme 1. Pure PB successful synthesis of PB nanocubes. Moreover, the TEM image
without PDA coating was calcined at 550  C with a heating rate of (Fig. 1b) demonstrated its nanocube morphology and solid feature
10  C min
1 and held for 1 h under N2 to prepare the N-doped obviously. All existed elements in energy dispersive X-ray
Fe3O4/C nanocages. spectroscopy (EDS) of PB nanocubes (Fig. 1d) contained C, N, O,
K and Fe further confirmed the synthesis of PB. The K element

Scheme 1. Schematic illustrating the preparation process of the HPHNF nanocomposites.

52 L. Wang et al. / Electrochimica Acta 186 (2015) 50–57

Fig. 1. (a) SEM and (b) TEM image of as-prepared PB, (c) EDS and (d) XRD pattern of PB.

Fig. 2. Low-magnified and high-magnified SEM images (a,b) and TEM images (c,d) of PB@PDA.
 L. Wang et al. / Electrochimica Acta 186 (2015) 50–57 53

Fig. 3. Low-magnified and high-magnified SEM images (a,b) and TEM images (c,d) of the HPHNF nanocomposites.

Fig. 4. (a) XRD pattern and (b) XPS spectrum of the HPHNF nanocomposites. (c) High-resolution XPS spectrum of Fe 2p. (d) Nitrogen adsorption/desorption isotherm for the
HPHNF. The inset is the pore size distribution of the HPHNF sample.
54 L. Wang et al. / Electrochimica Acta 186 (2015) 50–57

Fig. 5. (a) CVs of the HPHNF during the first three cycles at 0.2 mV s
1, (b) Galvanostatic charge/discharge profiles of the HPHNF electrodes for the 1st, 50th, 100th, 150th and
200th cycle at a specific current of 200 mA g
1. (c) Cycling performance of the HPHNF nanocomposites, N-doped Fe3O4/C nanocomposites and graphite at a specific current of
200 mA g
1. (d) Coulombic efficiency of HPHNF.

mainly originated from the residual K+ in K3[Fe(CN)6]. The XRD was the porous hollow nanocages (Fig. 3c). According to the HRTEM
performed to detect the crystal structure and phase purity of PB image (Fig. 3d), the PDA layer was transformed into N-doped
nanocubes. As shown in Fig. 1d, all diffraction peaks from the XRD porous carbon network and at the same time the Fe3O4 nano-
pattern could be assigned to the standard Fe4[Fe(CN)6]3 (JCPDS no. clusters were encapsulated completely by multilayer graphitic
73-0687) [32], suggesting the extreme purity of the prepared PB. carbon. The interplane spacing of 0.21 nm was assigned to the
Then PDA was coated on the above PB surface to prepare (4 0 0) crystalline planes of Fe3O4. In order to highlight the
PB@PDA. The low-magnification and high-magnification SEM superiority of the PDA coating, N-doped Fe3O4/C nanocages
images of as-prepared PB@PDA nanocubes are shown in Fig. 2a without PDA coating were also prepared by calcining pure PB
and b, respectively. Interestingly, the surface of PB@PDA became under the identical condition. SEM images (Fig. S1, Supporting
rough and was covered with many grooves. The average size of Information) revealed that Fe3O4/C possessed the similar mor-
PB@PDA was larger than that of PB correspondingly. TEM was phology to HPHNF after carbonization, but the cube surface inward
utilized to study the interior structure of PB@PDA. As revealed in shrinked to some extent.
Fig. 2c and d, the PB nanocubes were covered by the uniform PDA As shown in Fig. 4a, the XRD pattern of as-synthesized HPHNF
layer with a thickness of 10 nm. reveals detailed information relating to crystalline and purity. The
The PB@PDA nanocubes were subsequently carbonized under corresponding diffraction peaks at 30.1, 35.4 , 37.1, 43.1, 53.4 ,
550  C with a heating rate of 10  C min
1 and held for 1 h under N2 56.9 , 62.5 and 74.9 are assigned to the (2 2 0), (3 11), (2 2 2),
to obtain the well-defined HPHNF. It was clearly observed that the (4 0 0), (4 2 2), (5 11), (4 4 0) and (5 3 3) crystalline planes of Fe3O4
grooves on the surface of HPHNF became more apparent and many (JCPDS no. 19-0629), respectively [33]. No additional diffraction
cavities appeared after the carbonization as revealing by the SEM peaks were observed, revealing the high purity of Fe3O4 nano-
images of as-prepared HPHNF (Fig. 3a and b). We could even particles. The XPS (Fig. 4b) confirmed the presence of C, N, O, K and
observe interior hollow structure from the broken edges of HPHNF Fe. The high-resolution XPS profile of Fe 2p (Fig. 4c) showed two
after mechanical grinding (Fig. 3b). TEM image clearly indicated obvious peaks at 724.8 eV and 711.3 eV which corresponded to the
 L. Wang et al. / Electrochimica Acta 186 (2015) 50–57 55

h g
1, 753.8 mA h g
1 and 878.7 mA h g
1, respectively. The trend of

the specific capacity for metal oxide-based anode materials
decreasing firstly and then rising gradually was attributed to the
full activation as circulation proceeding.
The compare of the cycle performance of the HPHNF, Fe3O4/C
derived from pure PB and graphite were illustrated in Fig. 5c. The
HPNHF and Fe3O4/C delivered initial discharge capacities of
944.2 mA h g
1 and 917.8 mA h g
1, respectively. From the second
cycle, the HPHNF delivered a Coulombic efficiency of almost 100%.
The HPHNF electrode could maintain the reversible discharge
capacity of 878.7 mA h g
1 after 200 cycles at a specific current of
200 mA g
1, while the N-doped Fe3O4/C electrode only manifested
the reversible discharge capacity of 547.1 mA h g
1 and the typical
anode material-graphite dropped to 324 mA h g
1 after 100 cycles.
The cycling performance of the two Fe3O4-based materials was
much better than graphite due to the higher theoretical capacity
and unique structure. Two main factors might contribute to the
significant difference of the electrochemical performance between
HPHNF and N-doped Fe3O4/C. First, the smaller surface area (only
12.7 m2 g
1) of the N-doped Fe3O4/C resulted in longer Li+ diffusion
Fig. 6. Rate performance of HPHNF nanocomposites and N-doped Fe3O4/C distance and insufficient electronic contact between the electro-
nanocomposites from pure PB.
lyte and the active material as compared with HPHNF. Second, the
elastic and robust N-doped carbon network derived from the PDA
binding energies of Fe2p1/2 and Fe2p3/2, matching well with the
coating layer not only improved the conductivity of the active
previous reports of Fe3O4 [34,35]. The high-resolution XPS
material, but also created more defective site for lithium insertion.
spectrum of C 1s (Fig. S2, Supporting Information) showed four
Therefore, the HPHNF possessed outstanding cycling stability and
obvious peaks at 284.3 eV, 285.2 eV, 285.8 eV and 288.6 eV
superior rate performance.
belonging to C–C, C–N, C–O and O
C=O groups, respectively
The rate performances of the HPHNF and N-doped Fe3O4/C
[21]. The amount of N and C elements of HPHNF were estimated to
nanocomposites at various current densities were tested as one of
be 8.3 % and 43.5 % which were higher than of the N-doped Fe3O4/C
the most significant parameters. As shown in Fig. 6, the HPHNF
(2.9 % and 26.0 %) (Table S1, Supporting Information). The
released the reversible capacities of 775.5 mA h g
1, 683.4 mA h
Brunauer–Emmett–Teller (BET) surface area of HPHNF was
g
1, 518.5 mA h g
1, 386.5 mA h g
1 and 254.3 mA h g
1 under the
calculated to be 58.2 m2 g
1 through N2 adsorption/desorption
current densities of 100 mA g
1, 200 mA g
1, 500 mA g
1, 1 A g
1
measurements. However, the BET surface area of Fe3O4/C nano-
and 2 A g
1, much higher than that of the N-doped Fe3O4/C
cages was measured to be only 12.7 m2 g
1. The larger BET was
nanocomposites (only 712.3 mA h g
1, 520.2 mA h g
1, 275.6 mA h
mainly attributed to the surface modification of PDA layer which
g
1, 153.7 mA h g
1 and 78.8 mA h g
1). As the specific current
resulted in more micro/mesoporosites. According to the results of
backed to 200 mA g
1, the specific capacity of 759.1 mA h g
1 and
XRD, XPS and BET, the PB@PDA nanocomposites were totally
converted into HPHNF after the thermal treatment.
Table 1
To study the electrochemical mechanism, the first three CVs of Comparison of the electrochemical performance of Fe3O4-based materials as anode
the electrode made of the HPHNF (Fig. 5a) were performed over materials for LIBs.
potential window from 0.01 V to 3.00 V at a scan rate of 0.2 mV s
1.
Active material Specific Initial coulombic Nth References
In the first discharge process, an unobvious peak centered at 1.50 V current efficiency mA h g
1
might be caused by an irreversible lithium loss, corresponding to mA g
1 %
the decomposition of the electrolyte and formation of solid Hollow graphene/ 100 68.2 900 (50) [16]
electrolyte interphase (SEI) [22,36]. A prominent broad peak Fe3O4
locating at 0.50 V was ascribed to the reduction of Fe2+ and Fe3+ to CNTs/Fe3O4 100 61.6 836 [23]
Fe0 as well as the formation of Li2O. In the following discharge (100)
Graphene/Fe3O4 100 65.1 650 [37]
curves, the cathodic peak located at 0.50 V was shifted to 0.80 V
(100)
due to the polarization of the electrode material in the first Graphene/Fe3O4 700 65.3 600 [39]
discharge process [16,37,38]. In the initial charge process, a small (100)
peak centered at 1.10 V was detected and it was resulted from the Carbon-decorated 93 78.6 830 (50) [40]
interaction between Li+ and external oxygenic functional groups Fe3O4
3D Hierarchical 92.5 63.5 605 (50) [41]
[21,22]. Furthermore, one broad peak appeared at 1.75 V which was Fe3O4/Graphene
ascribed to the reoxidation of Fe metal [33,37,39]. Obviously, the CV Fe3O4-Graphene 200 65.5 637(60) [42]
curves nearly overlapped after capacity fading of the initial Garbon@Fe3O4 463 80 560 (80) [43]
discharge/charge process. The galvanostatic discharge/charge Uniform Fe3O4 500 66 1046 [44]
Hollow Spheres (100)
profiles of the HPHNF for the 1st, 50th, 100th, 150th and 200th
Porous hollow Fe3O4 100 75 700 (50) [45]
cycles at a specific current of 200 mA g
1 over voltage range from beads
0.01 to 3.00 V are presented in Fig. 5b. During the first discharge Hollow Fe3O4/ 200 66.7 940 (50) [46]
procedure, HPHNF exhibited an obvious voltage plateau at graphene
approximate 0.75 V owing to the decomposition of Fe3O4 and Hollow Fe3O4 926 78.8 851.9 [47]
microsphere (50)
the formation of Li2O. The electrochemical reaction mechanism of Hollow Fe3O4/C 185 66 987 (70) [48]
Li+ with Fe3O4 could be depicted as [23,40]: Fe3O4 + 8Li+ + 8e
$ 3 spheres
Fe0 + 4Li2O. The reversible capacities of 1st, 50th, 100th, 150th and HPHNF 200 70.1 878 This work
200th were obtained as 944.2 mA h g
1, 787.1 mA h g
1, 739.9 mA (200)
56 L. Wang et al. / Electrochimica Acta 186 (2015) 50–57

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