Nano Energy 48 (2018) 238–247

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Electrostatic interaction in electrospun nanofibers: Double-layer carbon T

protection of CoFe2O4 nanosheets enabling ultralong-life and ultrahigh-rate
lithium ion storage
Longhai Zhanga, Tong Weib, Zimu Jiangb, Chaoqun Liub, Han Jiangb, Jin Changb, Lizhi Shengb,
⁎
Qihang Zhoub, Libo Yuana, Zhuangjun Fana,b,
a
College of Science, Harbin Engineering University, Harbin 150001, China
b
Key Laboratory of Superlight Materials and Surface Technology, Ministry of Education, College of Material Science and Chemical Engineering, Harbin Engineering
University, Harbin 150001, China

A R T I C LE I N FO A B S T R A C T

Keywords: There are crucial demands for high power density and long-term cycling performance of Li-ion batteries (LIBs),
Lithium-ion batteries and the development of stable electrode material operating at high current densities still remains a challenge.
CoFe2O4 nanosheets Here we develop a novel strategy for the synthesis of flexible N-doped carbon nanofiber/CoFe2O4 film
N-doped carbon fibers (CoFe2O4@N-CNF) with a double-layer carbon protection by electrospinning, which possesses stable carbon
Binder-free anode
shell and honeycomb-like core with CoFe2O4 nanosheets embedded into conductive and interconnected carbon
nanosheets. The unique structure is beneficial for providing robust structural stability upon long-term cycling,
and offering nitrogen-rich interconnected mesoporous and conductive carbon matrix for fast charge and ion
transport. As a consequence, the optimized CoFe2O4@N-CNF exhibits a high reversible capacity of 858 mAh g−1
at 0.1 A g−1, excellent rate capability (306 mAh g−1 at 30 A g−1), and superior cycling stability up to 10,000
cycles with almost no capacity loss at 10 A g−1. We believe that this proposed methodology has a profound
impact on drastic improvements of various flexible energy storage devices.

1. Introduction
Achieving high energy density lithium-ion batteries (LIBs) along
with high power density and robust cycle life, have been recently
considered as ultimate aim for electric vehicles and grid-storage ap-
plications [1–3]. Recently, transition-metal oxides (FeOx, Co3O4, NiO,
etc.) have attracted tremendous attention as promising anode materials
for next-generation LIBs due to their high theoretical Li-storage capa-
cities [4–8]. However, intrinsically low conductivity of metal oxides
accompanied with large volume expansion and serious agglomeration
during the repetitive lithiation/delithiation process, would inevitably
lead to poor both power ability and cycling stability [9]. To overcome
these drawbacks, employing nanoscale electrode materials with the
designed morphologies (nanofibers and nanotubes) or hybridization of
metal oxides with nanocarbons, can be attributed to improving the
kinetics of charge transfer and alleviating the structural strain during
cycling to a certain extent [10–13]. However, due to high surface en-
ergy and abundant boundaries of nanosized active materials, the pre-
servation of structural integrity of the electrode upon external stress at
high current densities, still remains a big challenge. Moreover, the
preparation of the electrode containing high surface area of nanoma-
terials requires excessive conductive agent and binder, resulting in poor
utilization of active materials. Therefore, rational interface engineering
in metal oxides and carbon skeleton with an integrated uniform struc-
ture, regular electron/ion transport pathways, and strong tolerance to
stress change, is necessary in strong pursuit of high power LIBs with
reliable electrochemical stability [14–17].
To further improve the volumetric/gravimetric capacities of the
electrodes, the integrated electrodes containing 3D interconnected na-
nocarbon (CNT, graphene) conductive networks without metallic cur-
rent collector and polymer binder, are considered as promising building
blocks for energy storage devices such as lithium-ion batteries and su-
percapacitors [2,5,18–20]. Electrospinning technology can weave fi-
brous film with the stacked nanofibers in a random or organized
fashion. It is worth mentioning that metal oxide/carbon fibrous film can
be constructed by electrospinning and consequent post-treatment
[12,21–25]. Unfortunately, when used as electrodes in LIBs, a majority
of the electroactive materials embedded into the inner fibers cannot be

⁎
Corresponding author.
E-mail address: fanzhj666@163.com (Z. Fan).

https://doi.org/10.1016/j.nanoen.2018.03.053
Received 23 January 2018; Received in revised form 15 March 2018; Accepted 20 March 2018
Available online 24 March 2018
2211-2855/ © 2018 Elsevier Ltd. All rights reserved.
L. Zhang et al.
Fig. 1. Schematic and characterization of the as-electrospun inorganic and organic precursor-PAN fibers. a) Schematic illustration of the distribution of inorganic and
organic phase, and TEM images of the inorganic and organic precursor-PAN fibers after thermal treatment. b) SEM image of inorganic precursor-PAN fibers. c) IR
spectra of PAN, inorganic and organic precursor-PAN fibers.
effectively accessed by the electrolyte ions, resulting in low both spe-
cific capacity and rate capability. Therefore, further efforts should be
devoted to the design of metal oxide/carbon fiber film with excellent
structural stability, fast electron/ion transport pathways and easy ac-
cessibility of electrolyte ions, providing for high energy/power LIBs
even at harsh operating conditions [7,13,15,26,27].
Herein, as a proof-of-concept experiment, we design a self-standing
and binder-free film containing core-shell structured CoFe2O4@N-CNF
(N doped carbon nanofibers) by electrospinning as shown in Fig. 1a.
The microstructures and morphographies of hybrid fibers can be
regulated by different metal oxide precursors (organic or inorganic) and
heat-treatment. By using inorganic precursor, the resulting I-CoFe2O4@
N-CNF exhibits core-shell structure with honeycomb-like core con-
taining CoFe2O4 nanosheets embedded into carbon network and porous
carbon shell (~ 100 nm in thickness). The unique structure can effec-
tively prevent the aggregation of the CoFe2O4 nanosheets, maintain the
structure stability and mitigate volumetric expansion of the electrode
during cycling. Additionally, the interconnected 3D honeycomb-like
structure and pores in carbon shell derived from the evaporation of
crystalline water can provide fast Li ion diffusion pathways during the
lithiation/delithiation process. As a result, the I-CoFe2O4 @N-CNF
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Nano Energy 48 (2018) 238–247
exhibits high-rate capability (858 mAh g−1 at 0.1 A g−1, 306 mAh g−1
at 30 A g−1), and superior cycling stability up to 10,000 cycles with
almost no capacity loss at 10 A g−1.
2. Experimental section
2.1. Synthesis of the I-CoFe2O4@N-CNF film
All the chemicals used were analytical grade and used without
further purification. In a typical synthesis, 0.8 g of polyacrylonitrile
(PAN, Mw ≈ 150,000) 1 mmol of Fe(NO3)3·9H2O and 0.5 mmol of Co
(NO3)2·6H2O were dissolved in 10 ml of N, N-dimethylformamide
(DMF) with vigorous stirring for 3 h at 80 °C, a viscous, uniform and
brown precursor solution was obtained. In a typical electrospinning
process, the precursor solution was electrospun at a high voltage of
18 kV and at a flow rate of 0.3 ml h−1 (electrospinning equipment: TL-
Pro from TONGLI TECH, Shenzhen, China). The distance between the
needle (N7-gauge) tip and the drum collector was around 15 cm. The
collected film was dried at 60 °C in vacuum for 12 h. The dried film was
further stabilized in air at 220 °C (5 °C min−1) for 3 h, then heated up to
600 °C (1 °C min−1) for 1 h in N2, and the final annealed product was
L. Zhang et al.
denoted as I-CoFe2O4@N-CNF. For comparison, the precursor nanofi-
bers were also treated at 700 and 800 °C in N2, while all other condi-
tions remained the same.
2.2. Synthesis of hollow CoFe2O4 nanofiber
The above precursor nanofibers were annealed at 220 °C
(5 °C min−1) for 3 h, then heated up to 600 °C (1 °C min−1) in air for
1 h.
2.3. Synthesis of O-CoFe2O4@N-CNF film
PAN (0.8 g), Fe(acac)3 (1 mmol) and Co(acac)2 (0.5 mmol) were
dissolved in 10 ml of DMF to prepare precursor solution. After the
electrospinning process, the film was first annealed at 220 °C
(5 °C min−1) in air for 3 h and then heat-treated at 600 °C (1 °C min−1)
in N2 for 1 h.
2.4. Synthesis of N-doped carbon nanofiber film (N-CNF)
The pure PAN precursor fibers were calcined with the same process
for the synthesis of I-CoFe2O4 @N-CNF, and named as N-CNF.
2.5. Material characterizations
The microstructures of the as-prepared samples were characterized
by field-emission scanning electron microscope (SEM, Camscan
Mx2600FE) and transmission electron microscope (TEM, JEM 2010).
The phase structures of the composites were characterized using X-ray
diffraction (XRD, TTR-III), and the surface chemical composition was
measured though X-ray photoelectron spectroscopy (XPS, PHI-5700).
Pore structure of the samples was measured at 77 K using NOVA 2000
(Quantachrome, USA). Thermogravimetric analysis (TGA) was per-
formed on a Pyris Diamond TG/DTA thermogravimetric analyzer
(Perkin-Elmer Thermal Analysis) from room temperature to 800 °C
(10 °C min−1) under air flow. Fourier transform infrared (FT-IR) spectra
were recorded on a VERTEX 70 FT-IR spectrometer (Bruker) in a range
of 4000–650 cm−1. Raman spectra were collected using a Jobin-Yvon
HR800 spectrometer with 458 nm wavelength incident laser light.
2.6. Electrochemical measurements
The N-CNF, I-CoFe2O4@N-CNF and O-CoFe2O4@N-CNF films (~
1 mg cm−2) were directed used as the working electrode. CR2032-type
coin cells were fabricated by sandwiching a porous polypropylene se-
parator between the working electrode and Li metal foil (Cyprus Foote
Mineral, 99.98%, USA) in a high-purity Ar-filled glove box with both
the moisture and the oxygen contents below 0.5 ppm. The electrolyte
used here was 1 M LiPF6 in a mixed solvent of ethylene carbonate (EC)
and dimethylcarbonate (DMC) (1:1, v/v) as the electrolyte.
Galvanostatic discharge and charge cycling of the cells was conducted
by using a CT2001A tester (Wuhan, China) at several different rates
between cut-off voltage of 0.01–3.00 V (vs. Li+/Li). Cyclic voltammo-
grams (CV) and electrochemical impedance spectroscopy (EIS) mea-
surements were conducted with an AMETEK model 1470E coupled with
a 1400 CellTest System (Solartron analytical), and the EIS parameters
were fitted by using ZView software.
The Li+ diffusion coefficient in the electrode is calculated by the
following Equation [28,29].
2 lustrate unique layered structure, the carbon shell was removed by
RT
D = 0.5 ⎛ 2 2 ⎞ oxidation treatment of the I-CoFe2O4@N-CNF at 600 °C in air for 5 min
⎝ An F C σ ⎠ (1)
where R is the gas constant, T is the absolute temperature, A is the
electrode area, n is the electrons number, F is the Faraday constant, and
C is the molar concentration of Li+.
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Nano Energy 48 (2018) 238–247
3. Results and discussion
3.1. Phase separation and controlled morphography mechanism
Different homogeneous precursor solutions were prepared by
mixing organic (Fe(acac)3 and Co(acac)2) or inorganic (Fe(NO3)3·9H2O
and Co(NO3)2·6H2O) salts with polyacrylonitrile (PAN) in DMF. During
electrospinning of inorganic salt-PAN precursor, under high electric
field, the metal and NO3- ions move towards the inner and outer needle
nozzle, respectively, resulting in the occurrence of phase separation
(Fig. 1a). IR spectrum of PAN-Fe(NO3)3-Co(NO3)2 fiber precursor fur-
ther confirms only a broad adsorption of NO3- band at 1380–1350 cm−1
on the surface of fiber without other characteristic bands of Fe(NO3)3
and Co(NO3)2 (Fig. 1c), suggesting NO3- ions gathered on the surface of
the fiber due to the cation movement towards the outer under high
electric field. Therefore, the as-obtained fibers exhibit core-shell
structure after pyrolysis in N2 atmosphere. It is reasonable to deduce
that the carbon shell is mainly derived from the pyrolysis of PAN, while
the honeycomb-like core is formed through the evaporation of the
crystal water in inorganic salt. After replacing inorganic salt with or-
ganic salt, the spectrum of PAN-Fe(acac)3-Co(acac)2 fiber precursor
shows the characteristic bands of PAN, Fe(acac)3 and Co(acac)2, de-
monstrating no phase separation and uniform distribution of organic
phases in the polymer fibers. As a result, the as-prepared O-CoFe2O4@
N-CNF is solid fiber with uniform distribution of 5–10 nm CoFe2O4
particles, which is in agreement with previous findings [15]. In addi-
tion, when the inorganic salt-PAN fiber precursor was annealed in air,
the resulting CoFe2O4 fiber displayed an uniform tubular structure due
to Kirkendall effect based on high diffusion rate of ferrite and relatively
low oxidation of carbon with temperature (~500 nm in tube diameter
and ~ 50 nm in wall thickness, Fig. S1j-i) [4].
Further investigation of the microstructures of the I-CoFe2O4@N-
CNF is shown in Fig. 2. The I-CoFe2O4@N-CNF flexible film consists of
long and cross-linked fibers (＞50 µm in length and 600 nm ~ 1 µm in
diameter, Fig. 2a, and Fig. S1a-c). The interconnected carbon network
can provide continuous conducting paths for electron transfer, as well
as excellent structural stability during electrochemical process. Fur-
thermore, the cross-sectional SEM image of the I-CoFe2O4@N-CNF
displays a core-shell structure with honeycomb-like core and carbon
shell with the thickness of ~ 100 nm (Fig. 2b,c). Compared with the
solid O-CoFe2O4@N-CNF, the I-CoFe2O4@N-CNF possesses mesoporous
core with the pore sizes of 10–20 nm from the evaporation of the crystal
water in inorganic salt during heat treatment (Fig. S1g-i). Moreover,
there are some mesopores in the carbon shell derived from the escape of
volatile components such as H2O, CH4 and H2 etc during the pyrolysis
of the precursor (Fig. S2a,b), which is beneficial for fast Li ion diffusion
during charge/discharge process [30,31]. Further TEM images of the I-
CoFe2O4@N-CNF confirm the existence of carbon shell and core with
3D interconnected porous network after the removal of metal oxides by
acid treatment (Fig. 2d, and Fig. S2c). Interestingly, the carbon shell
was pierced by CoFe2O4 particles due to grain aggregation and growth
when the heat-treatment temperature was increased from 600 to 800 °C
(Fig. S3).
More interestingly, the carbonized PAN macromolecules lead to
formation of layered ladder-like structure during annealing (Fig. S2d),
resulting in ultrathin CoFe2O4 nanosheets (~ 20 nm) embedded into
carbon layers due to spatially confined growth of CoFe2O4 (Fig. 2e).
High-magnification TEM image of the I-CoFe2O4@N-CNF further con-
firms multi-layer structure with highly crystallized CoFe2O4 nanosheets
embedded into the carbon layers (Fig. 2f, and Fig. S4). To further il-
(Fig. 2g). The honeycomb-like core is constructed by cross-linked
carbon nanosheets (Fig. 2h), and the remained “footprints” are ob-
served in carbon layers after the removal of CoFe2O4 using acid treat-
ment (Fig. 2i). When the treated time increased from 5 min to 2 h in air,
L. Zhang et al. Nano Energy 48 (2018) 238–247

a b c

Honeycomb core

~100 nm

5 μm 200 nm 100 nm
Carbon shell

d e f CoFe2O4 nanosheet

0.28 nm

Carbon layer

300 nm 100 nm 2 nm

g h j

(311)
Removal of carbon shell

Intensity (a.u.)

(220)

(440)
(511)
20 nm

(400)
(111)

(222)

(422)

(620)
(533)
i
JCPDF no. 22-1086 / CoFe2O4

300 nm 20 nm 10 20 30 40 50 60 70 80
2 Theta (deg.)
Fig. 2. a-c) SEM images of the I-CoFe2O4@N-CNF, showing shell-core structure with honeycomb-like core. d-f) TEM images of the I-CoFe2O4@N-CNF (the inset shows
SAED pattern image), exhibiting CoFe2O4 nanosheets confined into multi-confined carbon layers. g,h) TEM images of the I-CoFe2O4@N-CNF after air-treatment at
600 °C for 5 min, and consequent acid-treatment (i). j) XRD pattern of the I-CoFe2O4@N-CNF.

carbon shell is fully oxidized, and the resulting CoFe2O4 hollow fiber is
consisted of interconnected highly crystallized CoFe2O4 nanosheets
(Fig. S5), further confirming spatially confined growth of CoFe2O4
during thermal-treatment.
X-ray diffraction (XRD) pattern of the I-CoFe2O4@N-CNF film con-
firms the existence of well crystallized CoFe2O4 (JCPDS no. 22-1086)
with a cubic spinel structure (Fig. 2j). The diffraction peak of the I-
CoFe2O4@N-CNF at 24° corresponding to the characteristic (002) re-
flection of graphite carbon is narrower than that of the N-CNF, meaning
Fe and Co as catalysts for the graphitization of carbon [32], which is
also confirmed by Raman analysis (Fig. 3a). The I-CoFe2O4 @N-CNF has
higher intensity ratio of the graphitic-induced (G) peak to the defect-
induced (D) peak (IG/ID) than that of the O-CoFe2O4@N-CNF and N-
CNF, exhibiting a relatively high degree of crystallinity and graphiti-
zation [2,33,34]. Moreover, the contents of CoFe2O4 (37.2 wt%) and
nitrogen (12.7 wt%) in the hybrid material were determined by ther-
mogravimetric analysis (TGA, Fig. S6) and X-ray photoelectron spec-
troscopy (XPS) analysis (Fig. 3b), respectively. In the N1s spectrum of
the I-CoFe2O4@N-CNF (Fig. 3c), three fitted peaks centered at 398.4 eV,
399.6 eV, and 400.6 eV, which are attributed to pyridinic N, pyrrolic N,
and graphitic N, respectively. The area percentages of the fitted peaks
are 47.9%, 35.9% and 16.2%, respectively, representing the content of
the corresponding three N species, which can enhance the conductivity
of the electrode, and create more defects for numerous diffusion
channels and active sites during Li ion insertion [2,13,35].
Compared with the O-CoFe2O4@N-CNF and N-CNF, nitrogen ad-
sorption-desorption isotherm of the I-CoFe2O4@N-CNF exhibits obvious
type IV isotherm (Fig. 3d), indicating the existence of mesoporous
structure. Pore size distribution of the I-CoFe2O4@N-CNF exhibits nu-
merous mesopores centered at 1.7–3.8 nm and 5–10 nm (Fig. S7a),
corresponding to mesopores in the carbon shell and honeycomb-like
core, respectively, which are consistent with TEM observations. Bru-
nauer-Emmett-Teller (BET) surface area of I-CoFe2O4 @N-CNF is
77.9 m2 g−1, about 6 times higher than those of O-CoFe2O4@N-CNF
(13.4 m2 g−1) and N-CNF (13.8 m2 g−1). Therefore, high surface area
and mesoporous structure are beneficial for the enhanced electro-
chemical performances by providing large electrode/electrolyte contact
surface, buffering the volumetric change and facilitating fast Li ion
diffusion during cycling.
3.2. Electrochemical characterization
Fig. S8 illustrates the cyclic voltammogram (CV) curves of the initial
three cycles of the I-CoFe2O4@N-CNF electrode at a scan rate of

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L. Zhang et al.
Fig. 3. a) Raman spectra of the I-CoFe2O4@N-CNF, O-CoFe2O4@N-CNF and N-CNF. b) XPS survey spectra of the I-CoFe2O4@N-CNF and c) N1s spectrum. d) N2
adsorption/desorption isotherms of the I-CoFe2O4@N-CNF, O-CoFe2O4@N-CNF and N-CNF.
0.1 mV s−1 between 0.01 and 3.00 V vs Li+/Li. Two reduction peaks at
0.75 and 1.37 V correspond to the conversion reaction of Fe3+ and
Co2+ to their metallic states and the formation of solid electrolyte in-
terphase (SEI) layer, as well as Li2O [36]. The broad oxidation peak at
around 1.6 V and a shoulder at higher potential observed in the first
anodic process are attributed to the oxidation of the Fe and Co to Fe3+
and Co2+, respectively. Interestingly, the CV curves for the 2nd and 3rd
cycle are nearly overlapped, indicating a good reversibility. The reac-
tion equation of CoFe2O4 during charge and discharge can be described
as follow [9,37]:
C oFe2 O4 + 8Li+ + 8e− ↔ Co + 2Fe + 4Li2 O (2)
The rate performance of the I-CoFe2O4@N-CNF electrode is illu-
strated in Fig. 4a,b. The I-CoFe2O4@N-CNF electrode can deliver an
initial reversible capacity of about 858 mAh g−1 at 0.1 A g−1. The large
irreversible capacity of 549 mAh g−1, corresponding to a Coulombic
efficiency of around 64.2%, can be assigned to the formation of a solid
electrolyte interface (SEI) film and other side reactions [38]. Even at a
very high rate of 30 A g−1, the reversible discharge capacity is found to
be stabilized at 306 mAh g−1, much higher than those of the O-
CoFe2O4@N-CNF and N-CNF electrodes, and other previously reported
results in the literature for Co/Fe oxide based anodes (Fig. 4c, and Table
S1)[10,12,38–44], indicating excellent rate capability due to the sy-
nergistic effect of porous structure and ultra-small CoFe2O4 nanosheets
embedded into carbon. Remarkably, after a high rate charge-discharge
test at 30 A g−1, the capacity of the electrode can recover to the initial
value at 0.1 A g−1, demonstrating good structural stability and ro-
bustness of the electrode. Although the capacities of the I-CoFe2O4@N-
CNF electrode at relatively low rates are less than those of hollow
CoFe2O4 fiber, I-CoFe2O4@N-CNF treated at 700 °C and I-CoFe2O4@N-
CNF treated at 800 °C (Fig. S9,11), the I-CoFe2O4@N-CNF exhibits the
best rate capability among them, implying good structural stability. The
cycling stability of I-CoFe2O4@N-CNF is also superior to I-CoFe2O4@N-
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Nano Energy 48 (2018) 238–247
CNF (700), I-CoFe2O4@N-CNF (800), O-CoFe2O4@N-CNF and N-CNF
electrodes, maintaining 567 mAh g−1 with a capacity retention of 96%
after 1000 cycles at 5 A g−1 (Fig. 4d, and Fig. S10).
To further investigate the unexceptional rate performance, the CV
curves at various scan rates from 0.5 to 10 mV s−1 were carried out as
shown in Fig. 5a. Generally, the relationship between the measured
current (i) and the scan rate (v) can be deduced from the following Eqs.
(3) or (4) [45–47].
i = av b (3)
log i = log a + b log v (4)
Here, a is a constant, b is a value ranging from 0.5 (diffusion controlled
process) to 1.0 (capacitive behaviour), and the b-value is given by the
slope of the log(i) versus log(v) plots. As shown in Fig. 5b, the b-values
are 0.71 and 0.76 for the reduction and oxidation peaks, respectively,
implying that the electrochemical reaction is controlled by the combi-
nation of capacitive and diffusion processes. The capacitive contribu-
tion can be calculated by distinguishing the fraction of capacitive be-
haviour (k1v) and diffusion process (k2v1/2) according to Eqs. (5) or (6)
[48–50].
i = k1 v + k2 v1/2 (5)
i (V )/ v1/2 = k1 v1/2 + k2 (6)
where k1 and k2 can be determined by the linear relationship between i/
v1/2 and v1/2. The capacitive contribution for the current response can
be calculated and summarized in Fig. 5c. With increasing scan rate, the
capacitance contribution obviously increases, and a high capacitive
contribution of 86% is achieved at 10 mV s−1. The corresponding CV
curves with the capacitive current (purple region) distinguished from
the total current at 10 mV s−1 are shown in Fig. 5d. High capacitive
contribution is mainly attributed to rapid Li+ ions insertion/extraction
kinetics due to the existence of some mesopores and shortened ion
L. Zhang et al.
Fig. 4. a) Rate capabilities of the I-CoFe2O4@N-CNF, O-CoFe2O4@N-CNF and N-CNF. b) Discharge/charge profiles of the I-CoFe2O4@N-CNF at various rates. c)
Comparison of rate performance for the I-CoFe2O4@N-CNF and previously reported high-performance Co/Fe oxide based electrodes. d) Cycling performances of the
I-CoFe2O4@N-CNF, O-CoFe2O4@N-CNF and N-CNF electrodes at 5 A g−1.
diffusion pathways, resulting in the intercalation pseudocapacitance
occurred on the surface of the electrode material, especially at high
rates.
Electrochemical impedance spectroscopy (EIS) is a useful technique
to study the electrode kinetics of anode [51]. Fig. S12 shows Nyquist
plots of I-CoFe2O4@N-CNF at various voltages at 0.1 A g−1. Based on
the equivalent circuit (Table S2), almost no variation in Ohmic re-
sistance (Rs) is indicative of the stabilization of SEI layers and sup-
porting the stable capacity behaviour of the electrode, while the ob-
vious variation in charge transfer resistance (Rct) is highly sensitive to
voltages [52–54]. Moreover, the structural stability of the I-CoFe2O4@
N-CNF electrode during ultralong-term cycling at 10 A g−1 was further
investigated by EIS measurements (Fig. 6a,b). Based on the equivalent
circuit, the Rct values obviously increase in the first 200 cycles, then
decrease sharply until 2000 cycles (Fig. 6b), corresponding to the po-
larization and activation of the electrode, respectively [9]. After 2000
cycles, the Rct and Rs values change little until 10,000 cycles, meaning
that the integrated fibrous film with core-shell structure possesses good
structural stability with cycling. Moreover, Li+ diffusion coefficients of
the I-CoFe2O4@N-CNF electrode are 0.39 × 10−15, 0.89 × 10−15,
1.35 × 10−15, 1.96 × 10−15, 1.26 × 10−15, 0.33 × 10−15 cm2 s−1
after 100, 200, 500, 2000, 5000, and 10,000 cycles (Fig. 6c),
243
Nano Energy 48 (2018) 238–247
respectively, a little change with cycling, further confirming its good
structural stability, as well as unique mesoporous architecture for fast Li
ion diffusion. As a consequence, the I-CoFe2O4@N-CNF shows a re-
versible specific capacity of 349 mAh g−1 with almost no capacity loss
after 10,000 cycles at a high rate of 10 A g−1. Such outstanding capa-
city/rate performance/cycling stability are far in excess of the other
reported Co/Fe oxide based anodes in the literature (Fig. 6d, and Table
S1)[9,10,12,36,41,55–62]. The significantly enhanced cycling stability
of the I-CoFe2O4@N-CNF can be attributed to the unique 3D structure.
(i) 3D conductive carbon network ensures fast electron transport, (ii)
the porous shell and honeycomb-like core facilitate ion diffusion
through the matrix, (iii) the integrated flexible film and elastic shell can
effectively accommodate the volumetric change during cycling and
maintain the integrity of electrodes, (iV) the confined carbon layers can
further prevent the self-aggregation and pulverization of CoFe2O4.
It is worth pointing out that the huge volume change of active
materials generally occurs during the lithiation/delithiaion process,
while maintaining the overall structural and conductive stability of the
electrode is essential to long-term cyclability and rate performance for
lithium ion batteries [63–65]. To further investigate microstructure and
phase structure change of the I-CoFe2O4 @N-CNF electrode with cy-
cling, electron microscopy, Raman and XRD measurements were
L. Zhang et al.
carried out. There is almost no change for the observed G peak in
Raman spectrum even after 500 cycles (Fig. 7a), showing stable carbon
shell of the I-CoFe2O4@N-CNF without obvious destruction of graphite
structure. After 5000 cycles, the increased G peak means the removal of
carbon shell and the newly exposed carbons with high graphitization.
Remarkably, the appeared 2D peak (2675 cm−1) and D+G peak
(2930 cm−1) of the I-CoFe2O4@N-CNF after 5000 cycles further con-
firm the existence of few-layered graphene [66]. Additionally, XRD
pattern of the I-CoFe2O4@N-CNF after 5000 cycles shows a very sharp
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Nano Energy 48 (2018) 238–247
Fig. 5. a) Cyclic voltammogram of the I-
CoFe2O4@N-CNF electrode at various scan rates,
and b) the relationship between peak current to
scan rate. c) Contribution ratio of the capacitive
and diffusion controlled processes at different scan
rates, and d) the capacitive contribution to charge
storage of the I-CoFe2O4@N-CNF electrode at
10 mV s−1.
and strong peak at 24° (Fig. 7b), corresponding to the (002) plane of
carbon, which further confirms high graphitization of carbon in the
core. Moreover, new phases of Fe2O3 and CoO from the conversion of
CoFe2O4 are observed, and the peak intensities of metal oxide decrease
due to the pulverization of CoFe2O4 nanosheets with cycling. Fig. 7c
shows the schematic illustration of morphological and structural
changes for the I-CoFe2O4@N-CNF after various cycles. In the initial
200 cycles, the film exhibits unbroken conductive network, and the
outer carbon shell of the fiber maintains its original structure (Fig.
Fig. 6. a) Nyquist impedance plots of the I-
CoFe2O4@N-CNF electrode (the inset shows
equivalent circuit model). b) Rct, Rs and cycling
performance of the I-CoFe2O4@N-CNF elec-
trode with cycling at 10 A g−1. c) The re-
lationship between Z′ and ω−1/2 in the low-
frequency region, and Li+ diffusion coeffi-
cients after cycling for the I-CoFe2O4@N-CNF
electrode. d) Comparison of capacity/rate
performance/cycling stability for I-CoFe2O4@
N-CNF and previously reported Co/Fe oxide
based electrodes.
L. Zhang et al.
a D G
CoO & Fe2O3 2D
Intensity (a. u.) 10000 cycles
3000 cycles
500 cycles
200 cycles
Before cycle
500 1000 1500 2000 2500 3000 3500 4000
Raman (cm-1)
c
200 cycles
d e
5000 Cycles
5 μm
g h
No pulverization
10000 Cycles 300 nm
Fig. 7. a) Ex-situ Raman spectra and b) XRD patterns of the I-CoFe2O4@N-CNF after various cycles at 10 A g−1. c) Schematic illustration of morphological and
structural changes with cycling. d-i) SEM and TEM images of the I-CoFe2O4 @N-CNF electrode after 5000 (d-f) and 10,000 cycles (g-i) at 10 A g−1.
S13a-c). With cycling, the carbon shell is gradually etched due to the
exfoliation of ultra-small carbon nanosheets under the repeated stress
(Fig. S13d,e). Completely disappeared carbon shell and exposed parti-
cles on the surface of the fiber are observed after 5000 cycles (Fig. 7d-f),
which are in agreement with above Raman and XRD analysis. After
10,000 cycles, some mesopores are formed again on the surface of the
fiber due to the repetitive Li ion bombardment (Fig. 7g), and carbon
etching gradually moves toward the fiber axis (Fig. 7h). It is worth
noting that ultra-small CoFe2O4 from the pulverization of CoFe2O4
sheets after 10,000 cycles are still embedded into carbon layers
(Fig. 7i), showing stable conductive network for superior rate capability
and cycling stability.
To our knowledge, this is among the best cycling stability reported
to date for LIBs. The excellent electrochemical performances of the I-
CoFe2O4@N-CNF are attributed to its unique core-shell structure.
Nano Energy 48 (2018) 238–247
b
5000 cycles 10000 cycles
f
200 nm 200 nm
i
200 nm 5 nm
Specifically, the skeletal N-doped carbon shell is beneficial for im-
proving the mechanical strength and conductivity of the electrode,
preventing the collapse of the core with cycling and the active materials
from being eroded by direct contact with the electrolyte, as well as
enhancing specific capacity through the defects in N-doping disordered
carbon. The honeycomb-like electrochemically active core, consisting
of ultra-small CoFe2O4 sheets homogeneously embedded into the
carbon sheets, can effectively accommodate the large volumetric
change of CoFe2O4 upon cycling. More interestingly, the interconnected
N-doped carbon sheets can not only offer high electronic conductivity,
but also efficiently prevent the self-aggregation of CoFe2O4 upon cy-
cling. Moreover, mesoporous structure can provide sufficient contact
between the active material and electrolyte, decrease Li ion diffusion
length and enhance electrochemical kinetics.
245
L. Zhang et al.
4. Conclusions
In summary, flexible core/shell I-CoFe2O4@N-CNF film with stable
carbon shell and electrochemically active honeycomb-like core, has
been developed as binder-free anode for high-performance LIBs. The
fibrous film with unique core-shell structure has robust structural sta-
bility, interconnected conductive network, CoFe2O4 nanosheets em-
bedded into carbon layers and mesopore channels. Benefiting from the
synergistic effects, the I-CoFe2O4@N-CNF film exhibits a high reversible
capacity, high-rate capability and superior cycling stability up to
10,000 cycles at 10 A g−1. Thus, this strategy proposed here will open a
new paradigm for the synthesis of fibrous hybrid film and broaden their
range of applications in supercapacitors, fuel cells and metal-ion bat-
teries.
Acknowledgements
The authors acknowledge financial support from National Natural
Science Foundation of China (51672055), Fundamental Research Funds
for the Central Universities (HEUCF201709), Natural Science
Foundation of Heilongjiang Province (LC2016017) and Ten Thousand
Talent Program (W02020249).
Appendix A. Supporting information
Supplementary data associated with this article can be found in the
online version at http://dx.doi.org/10.1016/j.nanoen.2018.03.053.
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Longhai Zhang is currently a Ph.D. candidate in the
College of Science at Harbin Engineering University (HEU)
under the direction of Prof. Zhuangjun Fan. His research
interests mainly focus on the synthesis of functional car-
bonaceous nanomaterials for energy storage (super-
capacitor, Li/Na-ion batteries).
L. Zhang et al.
Tong Wei received her Ph.D. in 2003 at the Institute of
Coal Chemistry, Chinese Academy of Sciences. She became
full professor at the College of Material Science and
Chemical Engineering, Harbin engineering University, in
2010. Her research interests focus on advanced nanoma-
terials for energy conversion and storage.
Zimu Jiang is currently pursuing Ph.D. in the College of
Material Science and Chemical Engineering at Harbin
Engineering University. His research interests mainly focus
on the synthesis of advanced nanomaterials for super-
capacitors and Li-ion batteries.
Chaoqun Liu is currently a master student in the College of
Material Science and Chemical Engineering at Harbin
Engineering University. His current research is focused on
the design and synthesis of functional carbonaceous mate-
rials for Li-ion batteries.
Han Jiang is currently a master student in the College of
Material Science and Chemical Engineering at Harbin
Engineering University. His current research interests in-
clude the design and synthesis of functional carbonaceous
nanomaterials as well as their applications for energy sto-
rage devices.
247
Nano Energy 48 (2018) 238–247
Jin Chang is currently a master student in the College of
Material Science and Chemical Engineering at Harbin
Engineering University. His current research is focused on
the design and synthesis of functional carbonaceous mate-
rials for energy storage devices.
Lizhi Sheng is currently pursuing Ph.D. in the College of
Material Science and Chemical Engineering at Harbin
Engineering University. His research interests mainly focus
on the synthesis of functional carbonaceous nanomaterials
for energy storage.
Qihang Zhou is pursuing Ph.D. in the College of Material
Science and Chemical Engineering at Harbin Engineering
University. Her current research is focused on the design
and synthesis of advanced nanomaterials for energy sto-
rage.
Zhuangjun Fan received his Ph.D. in 2003 at the Institute
of Coal Chemistry, Chinese Academy of Sciences. He be-
came full professor at the College of Material Science and
Chemical Engineering in 2006, and now he is the director of
the Institute of Advanced Carbon Based Materials at Harbin
Engineering University. His research interests focus on the
design and controlled synthesis of carbon nanomaterials
such as carbon nanotubes and graphene, and their appli-
cations in energy-related areas such as supercapacitors, Li-
ion batteries and full cells.