Carbon 111 (2017) 28e37

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Carbon
journal homepage: www.elsevier.com/locate/carbon

Enhanced cycle stability of polypyrrole-derived nitrogen-doped

carbon-coated tin oxide hollow nanofibers for lithium battery anodes
De Pham-Cong a, Jung Soo Park b, Jae Hyun Kim b, Jinwoo Kim c, Paul V. Braun c,
Jun Hee Choi d, Su Jae Kim a, Se Young Jeong a, Chae Ryong Cho a, *
a
Department of Nano Fusion Technology and College of Nanoscience and Nanotechnology, Pusan National University, Busan 609-735, South Korea
b
Division of Nano & Bio Technology, Daegu Gyeongbuk Institute of Science and Technology, Daegu 711-873, South Korea
c
Department of Materials Science and Engineering, Frederick Seitz Materials Research Laboratory, University of Illinois at Urbana-Champaign, IL 61801,
USA
d
Device & System Research Center, Samsung Advanced Institute of Technology, Samsung Electronics, Suwon 443e803, South Korea

a r t i c l e i n f o a b s t r a c t

Article history: SnO2 hollow nanofibers (SnO2 hNFs) are prepared through electrospinning and annealing processes. The
Received 17 July 2016 polypyrrole layers coated onto the surface of the SnO2 hNFs are annealed in a nitrogen atmosphere. The
Received in revised form nitrogen-doped carbon-coated SnO2 hNFs (SnO2/NC hNFs) are composed of SnO2 hNFs with a wall
19 September 2016
thickness of 60e80 nm and a nitrogen-doped carbon layer ~10 nm thick. The nitrogen content in the
Accepted 23 September 2016
carbon layer is approximately 7.95%. Owing to the nitrogen-doped carbon shell layers, the specific
Available online 28 September 2016
reversible capacity of SnO2/NC hNFs at a current density of 0.2 A g
1 after 100 cycles is 1648 mAh g
1,
which is 427% higher than that of (386 mAh g
1) SnO2 hNFs. This strategy may open new avenues for the
design of other composite architectures as electrode materials in order to achieve high-performance
lithium ion batteries.
© 2016 Elsevier Ltd. All rights reserved.

1. Introduction low cost, and environmental friendliness [7]. However, several

Rechargeable lithium ion batteries (LIBs) are the most promising
energy storage system for next generation potable electronic de-
vices and electric vehicles (EVs), which required further develop-
ment to provide high energy and power density with excellent
cycling stability [1e4]. Although LIBs with graphite as the anode
material have gained commercial success, their capacity is still
limited at low practical capacity compared to their theoretical
lithium ion storage capacity of 372 mAh g
1 [5]. In particular, their
high energy densities are very attractive for EV applications
because the energy density is directly related to the driving dis-
tance upon each charge. Recently, metal oxides (MxOy, M ¼ Sn, Fe,
Co, or Ni) have been attracting intensive attention as anode mate-
rials because of their high reversible capacity above 700 mAh g
1,
greatly spurring the rapid development of this field [6]. Among
these materials, SnO2-based nanostructured anode materials are
promising to replace commercial graphite with twice the theoret-
ical specific capacity (~782 mAh g
1) except for their abundance,
* Corresponding author.
E-mail address: crcho@pusan.ac.kr (C.R. Cho).
failure mechanisms lead to a fading specific capacity, such as: (i)
there is a large volume change (>300%) associated with the Li-ion
intercalation/deintercalation during the reaction process. Since
SnO2 can be generated the fracture due to the high-stress during
the volume expansion, (ii) the loss of contact between SnO2 active
materials and the carbon conductor during the repeated volume
change causes a capacity decay, and therefore SnO2 may be peeled
from the current collector, and (iii) the thickness of the solid elec-
trolyte interphase (SEI) layer on SnO2 continuously increases after
many cycles and volume changes. Consequently, the electrolyte can
be exhausted by the successive SEI layer growth [8,9]. Based on
these concerns, there is an urgent need to find the ideal nano-
structure of the hollow-type SnO2. This structure not only provides
easier Li ion transfer but also a lower strain during the volume
change, which results in a considerably improved cycle stability or
an enhanced specific capacity.
Conductive polymers (e.g., polypyrrole (Ppy) and polyaniline)
have been used as additives to improve the performance of anode
materials in LIBs, such as Si [10e12], Sn [13], SnS2 [14], SnO2 [15,16],
and TiO2 [17]. Conductive polymers can effectively buffer the vol-
ume changes during the cycling process and increase the

http://dx.doi.org/10.1016/j.carbon.2016.09.057
0008-6223/© 2016 Elsevier Ltd. All rights reserved.
 D. Pham-Cong et al. / Carbon 111 (2017) 28e37
Fig. 1. Schematic of the fabrication process to prepare the N-doped carbon-coated
SnO2 hNFs. (A colour version of this figure can be viewed online.)
Fig. 2. SEM images of (a) as-electrospun polymeric SnOx-based nanofibers, (b) SnO2 hNFs calcinated at 600  C, (c) conductive polymer Ppy-coated SnO2 hNFs, and (d) SnO2/NC hNFs
annealed at 600  C in nitrogen gas. The inset images display an enlarged view for each sample.
conductivity of the active materials. The conductivity of the poly-
mer depends on the reagent conditions, which may form a weaker
mechanical layer during the cycling process. On the other hand,
carbon coating onto the material may be a better method to
enhance the cycle lifetime of batteries. The conductivity of the
carbon layer can effectively increases the electrode conductivity,
control the SEI layer, and improve the surface chemistry of the
active material [18]. Another approach to improve the electro-
chemical performance of the carbon-coating layer is to modify its
surface functional groups with non-carbon elements, such as
29
nitrogen (N) and boron (B) [19,20]. The presence of heteroatoms in
the carbon layer may enhance the reactivity and electric conduc-
tivity, increasing of storage capacity of the anode material. N-doped
carbon materials (e.g., N-doped carbon nanotubes, N-doped gra-
phene, or N-doped turbostratic carbon) with a high conductivity,
distinct morphology, and specific surface properties have been
extensively applied in energy storage devices, including fuel cells,
LIBs, and Li-air batteries [21e24]. Nevertheless, the synthesis
methods for these materials may result in low nitrogen content or
an unstable doping of heteroatoms. To circumvent this problem,
pyrolysis of nitrogen-containing polymers or other compounds can
introduce nitrogen atoms into the carbon framework with durable
properties [25e27].
Based on these research trends, we have demonstrated a facile
method to obtain homogeneous graphene oxide-wrapped SnO2
hNFs with an improved cycling performance at a high current
density [28]. The graphene oxide networks can be supported to
provide a short electron pathway during lithium intercalation/
deintercalation in SnO2 hNFs; the composite exhibits a high Li-ion
storage capacity and an excellent rate performance. However, it still
has to overcome limitations, such as cycle lifetime and energy
density. Although there has been a great research effort on N-doped
carbon materials for energy storage, a SnO2 nanostructure with an
N-doped carbon coating layer is highly requested.
Herein, we designed a simple fabrication process for N-doped
carbon-coated SnO2 hNFs (SnO2/NC hNFs) utilizing the electro-
spinning and carbonization of conductive polypyrrole. We also
systematically investigated the microstructure and chemical
bonding states of SnO2 hNFs and SnO2/NC hNFs, focusing on the
behavior of N-doped carbon in electrically conductive supporting
materials.
2. Experimental
2.1. Synthesis of SnO2 hNFs
SnO2 hNFs were synthesized according to the procedure
30 D. Pham-Cong et al. / Carbon 111 (2017) 28e37
Fig. 3. (a) XRD patterns and (b) Raman spectra of SnO2 hNFs and SnO2/NC hNFs, and (c) the weight loss with respect to temperature of the as-electrospun polymeric SnOx-based
NFs, SnO2/PPy hNFs, and SnO2/NC hNFs. (A colour version of this figure can be viewed online.)
described in our previous work [28]. A transparent solution for
electrospinning was prepared by adding 1 g of SnCl2$2H2O to 5 mL
of N,N-dimethylformamide and 0.75 g of polyvinylpyrrolidone
(Mw ¼ 1 300 000 g mol
1), followed by stirring for 10 h at room
temperature. The solution was transferred to a plastic cylinder with
a stainless steel needle. The distance between the needle and the
aluminum collector foil was around 20 cm and the voltage that was
applied to the needle was 15 kV. The electrospun nanofibers were
calcinated at 600  C for 3 h with a heating rate of 3  C min
1, and
eventually crystallized.
2.2. Preparation of N-doped carbon-coated SnO2 hNFs
Using a micropipette, 0.4 g of the prepared SnO2 hNFs was
added in 0.5 mL of liquid pyrrole. The pyrrole molecules were
subsequently polymerized. The mixture was added to a 100 mL
ethanol solution containing 0.2 M FeCl3 under stirring and the re-
action continued for 24 h. The Ppy-coated SnO2 hNFs were sepa-
rated from the polymer solution by filtration. The sample was dried
in a vacuum oven at 50  C for 12 h. The Ppy-coated SnO2 hNFs were
annealed at 500  C for 3 h in N2 gas to form the N-doped carbon-
coated layer.
2.3. Characterization
The sample morphologies were characterized by scanning
electron microscopy (SEM; Hitachi, S4700) at an operating voltage
of 15 kV. The crystal structure of the materials was determined
using X-ray diffraction (XRD; Phillips, X'pert Pro) in the q-2q scan
mode, with 2q ranging from 10 to 80 , and CueKa1 radiation. To
investigate the reaction process according to the increasing tem-
perature of the as-electrospun polymeric nanofibers and to esti-
mate the carbon content in the SnO2/NC hNFs, thermogravimetric
analysis (TGA; TA Instruments, Q500) was performed from room
temperature to 800  C with a heating rate of 10  C min
1 in air. The
samples were characterized with microstructure and elemental
mapping using transmission electron microscopy (TEM; Jeol,
JEM2011). Raman spectra were obtained to identify the existence of
the carbon layer using a Raman spectrometer (Dongwoo Optron,
MonoRa500i) with a 514 nm excitation light source of an argon ion
laser. The chemical bonding states of the pristine SnO2 hNFs and
SnO2/NC hNFs were analyzed using X-ray photoelectron spectros-
copy (XPS; Thermo Fisher Scientific, ESCALAB250) with mono-
chromatic AleKa radiation (1486.6 eV). The binding energies in the
spectra were calibrated with carbon (C1s, 284.6 eV).
2.4. Electrochemical properties
The working electrodes were prepared by mixing a slurry of
active materials (SnO2 hNFs, SnO2/NC hNFs), carbon black, and
carboxymethyl cellulose (weight ratio of 70:15:15, respectively) in
deionized water as a solvent, then coated onto a copper foil. The
electrode was dried at 100  C in a vacuum oven to completely
remove the solvent. The amount of active material in each working
electrode disc was 1.1e1.3 mg cm
1. Test CR2032-type battery cells
were assembled using Li foil (D ~1.6 cm, t ~1.2 mm) as the counter
electrode and polyethylene film as a separator in a glove box
equipped with pure argon gas (99.999%). LiPF6 (1 M) in ethylene
carbonate/dimethyl carbonate (1:1 vol%) with 10% fluoroethylene
carbonate was used as an electrolyte. Galvanostatic cycling profiles
were recorded at a constant current between 0.001 and 3.0 V vs. Li/
Liþ at various current densities with a Wonatech 1000 battery
tester at ambient temperature.
3. Results and discussion
The fabrication process for the SnO2/NC hNFs is shown in Fig. 1.
The SneO based polymeric nanofibers featuring smooth surfaces,
were fabricated by electrospinning (Fig. 1a). The polymeric nano-
fibers were annealed at 600  C for 3 h in air (heating rate of 3  C
min
1) to remove the PVP polymer and then transformed to the
crystalline SnO2 hNFs (Fig. 1b). The formation of hollow-type SnO2
hNFs may be attributed to the free diffusion of ionic contents and
the gas released from the decomposition of the polymer [28,29].
The conductive pyrrole was used as a carbon precursor and the Ppy
layer was formed by the simple polymerization reaction of the
monomer pyrrole in a FeCl3 solution for 24 h (Fig. 1c). As a result, a
novel one-dimensional SnO2 hNFs coated with a N-doped carbon
layer was obtained by the carbonization reaction in N2 gas at 500  C
(Fig. 1d). The sample changed from the white color of SnO2 hNFs to
the black color of SnO2/NC hNFs because of the carbon-coated
layers (Supporting information, Fig. S1).
The SEM images of the samples are shown in Fig. 2. The inset
image for each figure shows an enlarged part of the sample. The as-
electrospun SnO2 NFs have an average diameter of 450 nm with a
smooth surface (Fig. 2a). Fig. 2b shows that the crystallized SnO2
hNFs are uniformly formed after removing the PVP polymer and
have a wall thickness of ~50 nm and grain size of ~80 nm. The shape
of the SnO2 hNFs did not change after the conductive Ppy coating
(Fig. 2c) and carbonization process (Fig. 2d).
Fig. 3 shows the structural properties and weight loss of the
sample with respect to the increasing temperature. As shown in
Fig. 3a, the XRD pattern of the SnO2/NC hNFs is similar to that of the
 D. Pham-Cong et al. / Carbon 111 (2017) 28e37 31

Fig. 4. XPS wide-scan spectra for (a) SnO2 hNFs and (b) SnO2/NC hNFs. High resolution XPS spectra of (c) Sn 3d, (d) C 1s, (e) O 1s, and (f) N 1s for the SnO2 hNFs and SnO2/NC hNFs.
(A colour version of this figure can be viewed online.)

pure SnO2 hNFs, in which all of the diffraction peaks can be
assigned to the Miller planes of the rutile phase of SnO2 [JCPDS card
no. 41-1445]. However, there is a difference in the peak intensity of
SnO2 due to the coating of the N-doped carbon layer.
There are no additional peaks of iron oxide, which indicates the
successful removal of iron-related components. Raman spectra
were measured at room temperature in the range of
300e1800 cm
1 for the SnO2 hNFs and SnO2/NC hNFs and are
presented in Fig. 3b. The peaks can be clearly divided into two re-
gions. The Raman peaks of SnO2 appeared in the range of
300e900 cm
1, with the highest peak located at approximately
632 cm
1, confirming the production of pure SnO2. The peaks at
475, 632, and 774 cm
1 correspond to the B2g, A1g, and Eg modes,
which are related to the doubly degenerate mode, asymmetric, and
symmetric stretching of SneO bonds, respectively [30]. The Raman
peak intensity of SnO2/NC hNFs in the range of 300e900 cm
1 is
lower than that of the pristine SnO2 hNFs due to the N-doped
carbon layers. Compared to the SnO2 hNFs, the only difference is
observed in the region of 900e1800 cm
1 for the SnO2/NC hNFs.
The characteristic peaks of carbonaceous materials are observed at
approximately 1352 and 1598 cm
1, corresponding to the disor-
dered D band (defect-related) and graphene G band (doubly
degenerate zone center E2g mode), respectively. The peak intensity
ratio between the D band and G band could be ascribed to a large
number of defects in the graphite structure [31,32]. There are no
carbon peaks in the region of 900e1800 cm
1 for the pristine SnO2
32 D. Pham-Cong et al. / Carbon 111 (2017) 28e37
Fig. 5. HRTEM images of (aec) SnO2 hNFs and (def) SnO2/NC hNFs at different magnifications. The N-doped carbon layer is visible on the SnO2 hNFs. (A colour version of this figure
can be viewed online.)
hNFs, confirming that the carbon content in the as-electrospun
SnO2 was completely removed during the annealing process. The
content of the polymer and carbon in the as-electrospun SnO2 hNFs
and SnO2/NC hNFs was determined by TGA with a heating rate of
10  C min
1 in air, as shown in Fig. 3c. The weight loss for the as-
electrospun SnO2 hNFs occurred mainly between 300 and 500  C
and remained constant above 500  C. The fraction of total weight
loss was about 64.5% compared to the initial weight. The weight
loss of SnO2/PPy hNFs was about 18% in the range of 300e500  C,
which corresponds to the oxidation of Ppy. Finally, the content of
the N-doped carbon layer coated onto SnO2 for the SnO2/NC hNFs
was approximately 10%.
Fig. 4a and b show the XPS wide-scan spectra of the SnO2 hNFs
and SnO2/NC hNFs, which reveal the chemical bonding states of
carbon, oxygen, tin, nitrogen, and chlorine. The Sn 3d spectra
(Fig. 4c) show two symmetrical peaks at 487.0 eV and 495.5 eV,
which are attributed to Sn 3d5/2 and Sn 3d3/2, respectively. The
peak-to-peak separation (spin-orbital splitting) between Sn 3d5/2
and Sn 3d3/2 is 8.5 eV, which corresponds to the 3d binding energy
of Sn4þ [33]. For the SnO2/NC hNFs sample, no peak shift was
observed in the Sn 3d spectrum, except for a decreased peak in-
tensity due to the coating layer. Furthermore, the C 1s peak was
deconvoluted to four peaks (284.4, 285.0, 286.4, and 288.1 eV),
which can be assigned to CeC, CeN, CeO, and C]N/C]O,
respectively [34]. The binding energy of the CeC bond for pristine
SnO2 hNFs is located at 284.4 eV and may be attributed to the ad-
hesive carbon tape used to hold the sample. The high-resolution
spectrum of O 1s for SnO2 hNFs, as shown in Fig. 4e, was decon-
voluted to the SneO and SneOH peaks located at 530.5 eV and
531.3 eV, respectively.
However, the binding energy of 532.1 eV for the SnO2/NC hNFs
was assigned to the CeO peak due to the coated carbon layer. A
strong N 1s peak, which was not detected for the SnO2 hNFs, was
only visible in the range of 396e403 eV for the SnO2/NC hNFs. Two
intense peaks could be distinguished and ascribed to pyridinic N
(398.6 eV) and pyrrolic N (400.4 eV) due to the Ppy network
[24,35e37]. The content of nitrogen in the SnO2/NC hNFs (7.95%) is
lower than that in the SnO2/Ppy hNFs (8.91%) (supporting infor-
mation, Fig. S2 and Table S1). It may be considered that the
carbonization process reduces the content of nitrogen species [38].
A large amount of chlorine (9.65%) was detected in the SnO2/PPy
hNFs due to the polymerization process of pyrrole, but it was
almost removed from the SnO2/NC hNFs after carbonization. The
nitrogen content considering only N and C element was SnO2/NC
hNFs (0 at%, 0 wt%), SnO2/Ppy hNFs (13.5 at%, 15.4 wt%) and SnO2/
NC hNFs(11.1 at%, 12.8 wt%), respectively.
High-resolution TEM (HRTEM) images of SnO2 hNFs and SnO2/
NC hNFs are presented in Fig. 5. As shown in Fig. 5a, the pristine
SnO2 hNFs were distributed homogeneously with diameters of
~500 nm. The wall thicknesses of SnO2 hNFs were in the range of
60e80 nm (Fig. 5b).
This hollow structure is efficient to increase the solid-electrolyte
interface area, which is more effective for Li ion diffusion than the
bulk material during the lithiation/delithiation process. The SnO2
hNFs were composed of polycrystalline SnO2 nanoparticles of
10e20 nm in length. The Fourier transformed selected area electron
diffraction (SAED) pattern shows lattice fringes with a d-spacing of
about 0.26 nm, which corresponds to the interplanar distance of
the (101) plane of tetragonal SnO2 (a ¼ 4.738 Å, c ¼ 3.187 Å)
(supporting information, Fig. S3) [39]. The elemental mapping of
Sn, O, and C was performed for the SnO2/NC hNFs, and each
element was uniformly distributed (supporting information,
Fig. S4). However, N was not clearly detected due to the limited
mapping resolution for the energy dispersive spectroscopy (EDS)
and the low N content. Notably, the specific surface areas of SnO2
hNFs and SnO2/NC hNFs were 36 and 42 m2 g
1, respectively
(supporting information, Fig. S5). The isotherm of the SnO2/NC
hNFs showed a slightly higher adsorption at a high relative pressure
 D. Pham-Cong et al. / Carbon 111 (2017) 28e37 33

Fig. 6. Electrochemical performance of the SnO2 hNFs and SnO2/NC hNFs as follows: (a, b) cyclic voltammetry at a scanning rate of 0.1 mV s
1, (c) specific capacity as a function of
cycle number at a current density of 0.2 A g
1, and (d, e) charge-discharge curves at a current density of 0.2 A g
1. (A colour version of this figure can be viewed online.)

(P/P0) range compared to the pristine SnO2 hNFs, indicating the broad peak located at approximately 0.2 V may be attributed to the
formation of a N-doped defective carbon layer on the SnO2 hNFs formation of LixSn following the lithiation/delithiation process
[35]. [40]:
The electrochemical performance of the SnO2-based electrodes
was evaluated using a half-cell battery test configuration with a SnO2 þ 4Liþ þ 4ee / Sn þ 2Li2O (1)
membrane between the synthesized active materials as the work-
ing electrode and lithium foil as the counter electrode. Fig. 6a and b Sn þ xLiþ þ xee 4 LixSn (0  x  4.4) (2)
show a cyclic voltammetry (CV) curve of the first three cycles of
SnO2 hNFs and SnO2/NC hNFs electrodes in the range of Liþ þ ee þ electrolyte / SEI (Li) (3)
0.001e3.0 V vs. Li/Liþ, respectively. In the first cathodic cycle of
Fig. 6a, strong peaks were observed at 1.23, 0.80, and 0.62 V related For the SnO2/NC hNFs sample, two cathodic peaks were located
to the formation of Sn and Li2O through the reduction of SnO2. The at 0.7 and 0.17 V, which contributed to the formation of the Li2O
34 D. Pham-Cong et al. / Carbon 111 (2017) 28e37
Fig. 7. (a) Rate capability at various current densities, (b) average specific capacity as a function of current density, and charge-discharge curves in the current density range of
0.1e3 A g
1 for (c) SnO2 hNFs and (d) SnO2/NC hNFs. (A colour version of this figure can be viewed online.)
layer. The formation of an SEI layer is commonly observed in the
initial cycle of anode materials. In the anodic curve, the three peaks
located between 0.4 and 1.0 V are attributed to Li dealloying from
LixSn, while the peaks at 1.25 and 1.82 V are attributed to the
oxidation of Sn and the decomposition of Li2O, as shown in SnO2
hNFs and SnO2/NC hNFs [41]. All peaks were reproducible and
stable after the first cycle, implying a good cycling stability of the
SnO2/NC hNFs. Fig. 6c shows the charge-discharge cycling perfor-
mance evaluated from 0.001 to 3.0 V at a current density of
0.2 A g
1. The SnO2/NC hNFs showed an excellent cycling stability
compared to the reported SnO2-based anodes (supporting infor-
mation Table S2). The discharge capacity increased to 127% after the
second cycles and 480% (1776 mAh g
1) after 120 cycles compared
to the theoretical capacity of graphite. This value is the highest
capacity reported for the SnO2-based anode material until now. On
the other side, the cycling performance of pure SnO2 hNFs dem-
onstrates a fast fading behavior of capacity from 1650 mAh g
1 at
the first cycle to 386 mAh g
1 at 100 cycles. Owing to the nitrogen-
doped carbon layers, the specific reversible capacity of SnO2/NC
hNFs at a current density of 0.2 A g
1 after 100 cycles
(1648 mAh g
1) is 427% higher than that of the SnO2 hNFs
(386 mAh g
1). These results may be associated with the enhanced
charge-transfer kinetics and the high reaction activity induced by
the N-doped carbon layer. As shown in Fig. 6d and e, the charge-
discharge curves for the specific cycle numbers of the SnO2 hNF
and SnO2/NC hNF electrodes were obtained under the voltage range
of 0.001e3.0 V vs. Li/Liþ at a current density of 0.2 A g
1, which is
the same condition as for Fig. 6c. The voltage plateau at 0.8e1.0 V
was observed for two samples at the first discharge step, which
stands the conversion reaction between SnO2 and Liþ leading to the
formation of Sn and Li2O [41]. The SnO2/NC hNFs electrode deliv-
ered specific capacities of 1835 and 1337 mAh g
1 for the first
discharge and charge cycles (the initial Coulombic efficiency was
approximately 72.8%). However, these values are still higher than
Coulombic efficiency (64.4%) and specific capacities (1583 and
1020 mA h g
1) at the first discharge and charge cycles for the SnO2
hNFs, respectively. The capacity loss during the first cycle may
generally be attributed to the irreversible formation of an SEI layer
on the surface of the hNFs and a small portion of the irreversible
conversion reaction of SnO2 into Sn during the first discharge
process. The Coulombic efficiencies were further increased to
approximately 100% for subsequence cycles, indicating the excel-
lent reversibility of the SnO2 hNFs and SnO2/NC hNFs electrodes.
The increase in capacity with increasing cycling could be attributed
to the activating process of the N-doped carbon-coated porous
structure of the anode. The formation of reversible gel-like poly-
meric layer was also considered as a reason of capacity increase
with cycling [42].
The rate capabilities of the anodes were tested under various
current densities, as shown in Fig. 7. The reversible capacities were
measured (Fig. 7a) when the charge-discharge current densities
were applied to two different electrodes and adjusted from
0.1 A g
1 to 3 A g
1 and back to 0.2 A g
1. A similar fading behavior
of the discharge capacity for two samples could be observed with
an increase of the current density. However, in the case of the SnO2/
NC hNFs, the average reversible capacity (746 mA h g
1) was still
higher than that of the pristine SnO2 hNFs (407 mA h g
1), even at a
high current density of 2 A g
1 (~2.5 C). Fig. 7b shows the variation
in the cell capacity according to the applied discharge rate, which is
expressed in A g
1. The data clearly showed that the SnO2/NC hNFs
electrode had a better rate capability. Here, the carbon and nitrogen
components in the SnO2/NC hNFs could enhance the electron
transfer and reduce the resistance related to the charge transfer
 D. Pham-Cong et al. / Carbon 111 (2017) 28e37 35

Fig. 8. Schematic of the lithiation/delithiation processes in both SnO2 hNF and SnO2/NC hNF electrodes. In the case of the SnO2/NC hNFs, several carbon layers containing the N-
doping, defects, and vacancies form on the surface of the SnO2 hNFs. (A colour version of this figure can be viewed online.)

through the electrode, showing a better performance than un-
coated electrode.
The charge-discharge curves over the voltage window of
0.001e3.0 V vs. Li/Liþ (ranging from 0.1 A g
1 to 3 A g
1) for the
SnO2 hNFs and SnO2/NC hNFs are shown in Fig. 7c and d, respec-
tively. The capacity at a low current density of 0.1 A g
1 in SnO2/NC
hNFs was approximately two times higher than for the pristine
SnO2 hNFs. The charge capacity of the samples after the first cycle
was higher than the theoretical capacity (782 mAh g
1) at a low
current density of 0.1 A g
1. This extra capacity is likely due to the
subsequent formation of an organic layer on the surface of the SnO2
hNFs [43]. Furthermore, compared to the SnO2 hNFs, the capacity of
the SnO2/NC hNFs may be enhanced due to the contribution of
nitrogen within the carbon layer the up to the 50th cycle at an high
current density of 1 A g
1 (supporting information, Fig. S6).
The excellent cycling stability and rate capability of the SnO2/NC
hNFs might be attributed to the rational design and engineering of
the unique nanostructure, as illustrated in Fig. 8. In this work, we
found that the N-doped carbon layer plays an important role in
significantly enhancing the electrochemical performance during
the cycle due to the greater number of defect sites in the layer
[44e47]. The N-doped carbon layer can be considered as a layer-by-
layer stack of the modified graphenes, which includes the nitrogen
element connected to the carbon lattice edges.
First, the 1D nanostructure of the SnO2 hNFs and their coated-
carbon layer could serve as a faster channel for electron transport
than the uncoated SnO2 hNFs. The coated-carbon layer also plays an
important role by increasing the contact points between the active
material and conductive carbon black electrolyte, which leads to a
sufficient electrode/electrolyte interface to absorb Liþ and pro-
motes a rapid charge-transfer reaction. Moreover, the in-
terconnections between the hNFs provide continuous pathways for
electron transport. The resistance of the SnO2/NC hNFs provided by
the EIS measurement before and after the long cycling is lower than
that of the SnO2 hNFs (supporting information, Fig. S7). In addition,
the electrochemical surface area is proportional to the capacitance
of the electrode-electrolyte interface. Defect sites and vacancies as
Liþ active sites would be extended gradually and thereby facilitate
more intercalation of Liþ [48,49]. The vacancies could trap a num-
ber of Liþ ions at the first cycle, and then these vacancies would be
extended during the following cycle and facilitate the insertion of
more Liþ ions. The capacity of the SnO2/NC hNFs increased due to
the number of defect sites and vacancies in the N-doped carbon
layers. From these results, we believe that the SnO2/NC hNFs with a
high content of nitrogen atoms show a higher reversible capacity
and longer cycling life compared to the pristine SnO2 hNFs.
4. Conclusions
We demonstrated the synthesis of SnO2 hNFs through a simple
36 D. Pham-Cong et al. / Carbon 111 (2017) 28e37
electrospinning and annealing process. N-doped (7.95%) carbon-
coated SnO2 hNFs were successfully formed by the carbonization
of the conductive polymer Ppy as anodes for LIBs. We found that
SnO2/NC hNFs exhibited a high specific capacity (1776 mAh g
1 at
120 cycles at a current density of 0.2 A g
1) and a good capability
(391 mAh g
1 at a current density of 3 A g
1). This result might be
considered due to the trapping phenomenon of Liþ in N-doped
carbon-coated layers and the high efficiency carrier transport effect
of the carbon-coated hNFs. Therefore, this study suggests that
SnO2/NC hNFs could be a promising anode material with a high
energy density and enhanced cycle stability for LIB applications.
Acknowledgement
This work was supported by a research program (grant NRF-
2015R1D1A3A01018611) through the Ministry of Education.
Appendix A. Supplementary data
Supplementary data related to this article can be found at http://
dx.doi.org/10.1016/j.carbon.2016.09.057.
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