Nano Energy 32 (2017) 397–407

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In situ analysis of SnO2/Fe2O3/RGO to unravel the structural collapse MARK

mechanism and enhanced electrical conductivity for lithium-ion batteries
⁎ ⁎
Kangsoo Leea,b, Seoyoon Shinb, Thomas Degenc, Wooyoung Leea, , Young Soo Yoonb,
a
Department of Materials Science and Engineering, Yonsei University, Shinchon-dong, 262 Seongsanno, Seodaemoon-gu, Seoul 120-749, Republic of Korea
b
Department of Chemical & Biological Engineering, Gachon University, Seongnamdaero 1342, 461-710 Gyeonggi-do, Republic of Korea
c
PANalytical B.V., Lelyweg 1, 7603 EA Almelo, The Netherlands

A R T I C L E I N F O A BS T RAC T

Keywords: Herein, we describe a microwave-assisted hydrothermal process to synthesize α-Fe2O3 nanotubes/SnO2

Iron oxide nanorods/reduced graphene oxide (FNT/S/RGO) for application as a high-performance anode in lithium-ion
Tin oxide batteries (LIBs). The composite products exhibit anisotropic growth because of heteronucleation and the
Reduced graphene oxide preferred orientation of SnO2. SnO2 nanorods on the FNT surfaces are converted into Sn metal during the
Nanoparticles
alloying/dealloying reaction, which offers improved electrical conductivity. The FNT/S/RGO show substantially
Anode
enhanced electrochemical properties because of the reduced volume expansion effect, which improves the
Li ion battery
electrical and Li-ion conductivity and provides a large surface area. As a consequence, the FNT/S/RGO anode
delivers a high reversible capacity of 883 mA h g−1 even at a current density of 200 mA g−1, with a capacity
retention of 90% between the 1st and 220th cycles, excellent high-rate capacity (382 mA h g−1 at 4320 mA g−1),
and long-term cycle durability (maintaining 629 mA h g−1 at 1000 mA g−1 for 1000 cycles). The presented FNT/
S/RGO electrodes are the most efficient SnO2- and Fe2O3-based anode electrodes reported thus far for LIBs. The
origin of the synergistic effect and the reaction mechanism of the FNT/S/RGO was thoroughly investigated
using various in situ transmission electron microscopy, electrochemical impedance spectroscopy, and X-ray
diffraction analysis methods.

1. Introduction considerable interest because of their excellent resistance to volume

expansion and short diffusion lengths for Li ions [10]. Nevertheless,
Iron oxide and tin oxide are considered promising anode materials one of the drawbacks of preparing hollow structures is the formation of
because of their high theoretical capacity (Fe2O3 and SnO2: ~1005 and a hard template during preprocessing, which is a tedious task because
~781 mA h g−1), eco-friendly materials, and natural abundance, which of the difficulty in obtaining a hollow nanostructure. The hard template
can be much higher than that of a commercial graphite anode from the hollow nanostructure is difficult to remove while keeping the
(372 mA h g−1) [1,2]. However, one of the serious drawbacks of metal hollow nanostructure intact. Synthesis without a template by calcina-
oxides, including Fe2O3 and SnO2, for LIBs is their low electrical tion is favorable. Therefore, in this study, we investigate the hollow
conductivity and severe volume expansion during the insertion and nanostructure of template-free α-Fe2O3 nanotubes/SnO2/RGO (FNT/
extraction of Li ions, which can result in the detachment of the metal S/RGO) prepared using a microwave-assisted hydrothermal process to
oxide anode from the current collector. This issue is directly related to a maximize the practical use and large-scale processability of Fe2O3
large initial capacity drop, poor rate capability, and insufficient cycle nanotubes and SnO2 nanorods as anode materials for LIBs.
performance [3]. Various groups have suggested solutions to these Recently, SnO2–Fe2O3 composites have been reported to exhibit
serious problems by designing structures such as nanorods, nanotubes, better cycling characteristics than pristine SnO2 or Fe2O3 due to the
nanocubes, nanoparticles, 3d porous structures, hollow shells, and presence of metallic components during conversion reaction [5,11].
epitaxial growth structures; however, all these solutions provide However, the electrochemical performance of simply mixed SnO2–
unsatisfactory rate capacity and long‐term cyclability [4–9]. Fe2O3 composites is unsatisfactory because of the huge volume changes
Because the high rate capacity and long‐term cyclability remain and low electrical conductivity in SnO2 and Fe2O3 during the reaction
unsatisfactory, hollow nanostructures to prevent volume expansion [5,8,12]. In the present work, the unique hybrid structure of FNT/S/
and provide high rate capability for metal oxide anodes have attracted RGO is proposed to overcome these drawbacks. To reduce the volume

⁎
Corresponding authors.
E-mail addresses: wooyoung@yonsei.ac.kr (W. Lee), benedicto@gachon.ac.kr (Y.S. Yoon).

http://dx.doi.org/10.1016/j.nanoen.2016.12.058
Received 9 November 2016; Received in revised form 7 December 2016; Accepted 30 December 2016
Available online 31 December 2016
2211-2855/ © 2017 The Authors. Published by Elsevier Ltd.
This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/BY-NC-ND/4.0/).
K. Lee et al. Nano Energy 32 (2017) 397–407

change, α-Fe2O3 nanotubes were fabricated with the free space of a contained a liquid electrolyte; the advantages of this approach are easy
hollow structure, which can offer superior and stable cyclability. The fabrication, applicability to any conventional transmission electron
Fe2O3 and SnO2 structure was synthesized as hollow α-Fe2O3 (wall microscope, and similarity to a realistic measurement environment
thickness of ~20 nm) and SnO2 nanorods (rod diameter of ~10 nm) to because of the liquid electrolyte [19,20]. Furthermore, the electro-
apply electric vehicle, hybrid electric vehicle and energy storage chemical characterization during cycling strongly affects the electron
systems, which can provide high rate performance [12]. In addition, conductivity, conversion mechanism, and structural integrity.
the RGO provides advantages such as improved electrical conductivity, Therefore, various in situ analysis techniques (TEM, electrochemical
a buffer effect, and a large surface area to accommodate Li ions [13,14]. impedance spectroscopy (EIS), and XRD) were used to examine the
Therefore, the synergistic improvement provided by RGO and FNT/S cycle mechanism of α‐Fe2O3 and SnO2. Profound insights of the
compared to pristine α‐Fe2O3 and SnO2 enables high capacity reten- reaction behavior and conversion mechanism of Fe2O3 nanotubes
tion, enhanced rate capability, and good cycle durability. and SnO2 nanorods were obtained.
The electrochemical performance of an anode, such as its cyclabil-
ity, rate capability, and coulombic efficiency, are strongly related to the 2. Experimental section
charge transfer and ion diffusion behavior at the electrode surface [15].
The formation of the solid electrolyte interface (SEI) on a complicated 2.1. Preparation of α-Fe2O3 nanotubes (FNTs)
shape and the co-relationship between the collapse mechanism and the
structural strain of the multi-metal oxide, which is generated from the All chemicals in this study were of analytical reagent grade. The
shape, remain difficult to define. Recently, in situ TEM conducted using FNTs were fabricated using a microwave‐assisted hydrothermal pro-
a bias-controlled in situ TEM holder revealed structural changes during cess (MARS 6, CEM Co.). FeCl3·6H2O, NH4H2PO4, and Na2SO4 were
lithiation; however, examining both the behavior of the decomposed mixed in 40 ml of deionized (DI) water, and the resulting solution was
electrolytes and the practical structural failure due to the use of a solid- transferred to a Teflon vessel and heated at 220 °C for 30 min. After the
type electrolyte or ionic liquid is difficult [16–18]. Therefore, FNT/S/ synthesis was complete and the mixture was cooled to room tempera-
RGO electrodes were characterized using stacked graphene sheets that ture, the precipitate was centrifuged with DI water and dried in an

Fig. 1. TEM images and schematics of the microwave-assisted hydrothermal synthesis process of (a) FNT at 220 °C, (b) FNT/S at 150 °C, and (c) FNT/S at 220 °C.

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Fig. 2. SEM images of (a) FNT, (b) FNT/S, and (c) FNT/S/RGO, (d) TEM image of the top (left) and side view (right) of FNT/S, (e) dark-field TEM image of the ion-sliced FNT/S
specimen, (f) high-resolution TEM image of SnO2 nanorod of FNT/S/RGO (enlarged image of boxed area from (e)), and fast Fourier transform (FFT) analysis (inset), (g) schematic of
the ion-slicing process of FNT/S for a TEM investigation of FNT/S/RGO, (h) TEM image of ion-sliced FNT/S/RGO, (i), (j), and (k) EDS mapping images of (h) for Sn, Fe and O,
respectively.

electrical oven at 70 °C for 12 h. 2.3. Preparation of α-Fe2O3 nanotube/SnO2/RGO (FNT/S/RGO)

FNT/S/RGO was fabricated in a two‐step microwave‐assisted

hydrothermal process. First, an FNT solution and RGO powder were
2.2. Preparation of α-Fe2O3 nanotube/SnO2 (FNT/S) concurrently synthesized at 220 °C for 30 min, centrifuged, and dried.
This synthesis was performed to improve the dispersion of the FNTs on
FNT/S was synthesized in a microwave‐assisted hydrothermal RGO (Fig. 1) compared to that achieved through the separate synthesis
process at 220 °C for 5 min with FNTs, SnCl4·5H2O, and NaOH in of FNT and RGO [21]. Second, a powder with SnCl4·5H2O, and NaOH
40 ml of DI water. The precipitate was centrifuged with DI water and in 40 ml of DI water was produced in a microwave-assisted hydro-
dried. thermal process at 220 °C for 5 min.

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2.4. Materials characterization (BioLogic EC‐Lab, VSP‐300) was performed at AC frequencies from
4 MHz to 100 mHz during the charge and discharge processes.
The surface morphology and structure of the FNTs, FNT/S, and
FNT/S/RGO were investigated using field-emission scanning electron
microscopy (FE‐SEM, Hitachi S‐4200 system) and high‐resolution 3. Results and discussion
TEM (HR‐TEM, JEM‐ARM200F, JEOL microscope). XRD and in situ
XRD (PANalytical) were conducted for crystal structure analysis. The 3.1. Materials design and structural characterization
specimen for HR-TEM was prepared using an ion slicer (JEOL ION
SLICER, EM-09100IS) at 6 kV and a glancing angle of 4°. To define the Fig. 1 presents the synthesis procedure for the FNT, FNT/S, and
weight ratio of FNT/S/RGO, simultaneous thermal analysis (STA, FNT/S/RGO nanostructures. The TEM image and a schematic of the
PerkinElmer, STA8000) was performed in air with a ramp rate of unique α-Fe2O3 nanotube (Fig. 1a) and SnO2 nanorods (Fig. 1b and c)
10 °C min‐1 from 25 to 1000 °C. The nitrogen adsorption isotherms prepared by a microwave-assisted hydrothermal process are shown.
and Brunauer–Emmett–Teller (BET, Micromeritcs ASAP 2020 analy- The formation mechanism of FNT/S is explained as occurring in two
zer) surface areas were examined. XPS (Thermo VG, U.K.) was steps. First, an SnO2 nucleus nucleated on the surface of the α-Fe2O3
conducted to characterize the bonding state and elemental distribution. nanotubes to decrease the lattice incongruity [22]. SnO2 nanorods have
a preferred orientation of [001]. Second, SnO2 nanorods were aniso-
tropically formed by the dehydration of Sn(OH)62- ions as hierarchical
2.5. Electrochemical characterizations heteronanostructures. The SnO2 nanorod formation is related to the
holding temperature control. When the holding temperature was
FNT, FNT/S, and FNT/S/RGO were prepared using the active increased from 150 to 220 °C, the length of the SnO2 nanorods
material (70 wt%), polyvinylidene fluoride as the binder (20 wt%), and increased between the outer and inner sides of the α-Fe2O3 nanotubes,
carbon black (10 wt%) with 1‐methyl‐2‐pyrrolidinone to characterize as shown in Fig. 1b and c.
their electrochemical performance. The prepared FNT, FNT/S, and Fig. 2 shows the nanostructure and growth behavior of the FNT,
FNT/S/RGO electrodes were assembled into coin cells (CR2032) using FNT/S, and FNT/S/RGO, as investigated by SEM, TEM, and energy-
Li foil and 1 M LiPF6 in EC: DEC (1:1) as the electrolyte in an argon dispersive X-ray spectroscopy (EDS). The SEM image of the FNTs
(purity: 99.999%)-filled glove box maintained at a humidity level below (Fig. 2a) shows their homogeneous length and their hole size. The
6 ppm. The coin cells were rested for 4 h to stabilize the open-circuit FNT/S specimens (Fig. 2b) show the uniform growth of SnO2 nanorods
voltage (OCV) and were subsequently cycled between 0.01 and 3 V on the FNT surface, which was synthesized at 220 °C, as noted in Fig. 1.
using a battery cycler (WBCS3000) at room temperature (~298 K). The The anchored FNT/S (Fig. 2c) was homogeneously distributed on the
in situ XRD pattern of FNT/S/RGO was recorded in the 2 theta range RGO sheets, which likely facilitated the formation of anchoring of FNT/
of 26 – 38° in order to investigate main peak of Fe2O3 and SnO2. The S as a heterogeneous nucleation site. The TEM image of FNT/S
FNT/S/RGO electrode for in situ XRD was consisted of specialized (Fig. 2d) shows an outer diameter (including SnO2 nanorods) of
equipment such as beryllium glass of 500 µm thick, O-ring sealed ~230 nm and a length of ~660 nm. The TEM specimen of FNT/S
Teflon pot, and SUS packages. FNT/S/RGO electrode was assembled was vertically milled using an ion slicer (Fig. 2g) to examine the
by same materials of Li foil, electrolyte, and separator. In situ EIS internal structure. The SnO2 nanorods were uniformly formed in a

Fig. 3. Structural analysis of FNT/S/RGO: (a) the refinement plot shows the measured data in red, the total calculated profile in blue, and the background curve in green; the bottom
difference plot shows the difference between calculated and observed data in red. The peak positions and intensities of the α-Fe2O3 phase peaks are displayed as green lines; the peaks of
the SnO2 phase are shown as blue lines. (b) Stephens model strain distribution plot based on the refined Stephens coefficients of the SnO2 phase. (c) Schematic of the Stephens's model of
the FNT/S/RGO structure. (d) Raman spectra of FNT/S/RGO.

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microwave hydrothermal process at the surface and inner site of the Typically, there are 3 (cubic) to 14 (triclinic) refinable coefficients,
FNTs, as shown in the cross-sectional dark-field TEM image of Fig. 2e. depending on the space-group symmetry. In addition, the SnO2 phase
Moreover, the HR-TEM images (Fig. 2f) of an SnO2 nanorod confirm shows a pronounced anisotropy of the peak full-widths at half-maxima
its crystalline nature (lattice fringes). The fast Fourier transform (FFT) (FWHMs). The peak half-widths slowly increase with increasing
pattern (inset of Fig. 2f) was indexed to the (200) and (101) planes of diffraction angle and depend on the crystallographic direction of the
the tetragonal SnO2 phase. In addition, the growth direction of the reflections. To model this directional {hkl} dependence of the peak
tetragonal SnO2 nanorod was the [001] direction, as determined from half-widths, we applied the Stephens model [29]. The Stephens model
the lattice image obtained via HR-TEM and FFT analysis. EDS analysis is a phenomenological description of the anisotropy of the peak half-
revealed that the FNT/S was composed of Sn, Fe, and O, as shown in widths because of microstrain in the crystallites; it has been widely
the TEM element mapping images (Fig. 2h–k). The SEM images of used by the Rietveld community and is implemented in many software
FNT/S reveal the optimization procedure of holding time control (Fig. packages. Thus, it fits the occurring variations in peak widths without
S4) and temperature control for the hydrothermal process (Fig. S5) to explaining the physical cause. (Details of the Caglioti function are
maximize the homogeneous growth of SnO2 nanorods on the FNT explained in the supporting text).
surfaces. The use of the Stephens model finally enabled a decent fit of the
The XRD patterns of FNT, FNT/S, and RGO were characterized, as data. The final refined Stephens model coefficients of the SnO2 phase
shown in Fig. S1. The XRD peaks of FNT were matched by α‐Fe2O3 are shown in Table S5. On the basis of these coefficients, we calculated
(a=b=5.038 Å, c=13.776 Å, JCPDS No. 01–089–0598). The sharp a strain distribution plot (pseudo-3D surface plot), as displayed in
diffraction peaks of α‐Fe2O3 clearly indicate that the FNTs have a Fig. 3b and c. A uniform microstrain distribution resulted in a sphere.
crystalline structure. The diffraction peaks of FNT/S coexist with those Therefore, stronger peak width anisotropy of the SnO2 nanorod
of the tetragonal SnO2 (a = b =4.73 Å, c =3.18 Å, JCPDS No. 01-088- indicates a more deformed sphere. The SnO2 nanorods should exhibit
0287) and the α‐Fe2O3 phases. The RGO sheet shows no evident XRD weaker structural integrity than the Fe2O3 nanotubes during the
pattern, which implies that the oxygen group of the GO sheet is insertion/extraction reaction because of the microstrain induced by
substantially reduced [23]. anisotropic grain growth.
To examine the crystal structure and growth behavior of FNT/S/ Raman spectroscopic analysis was conducted to further confirm the
RGO, Rietveld refinements were conducted, as shown in Fig. 3a. A composition of the FNT/S/RGO. The Eg modes of Fe2O3 appeared at
quantitative two-phase Rietveld analysis [24,25] was performed on the 292, 408, and 607 cm−1 [30]. Moreover, a small blue-shift of the FNT/
XRPD data of “specimen XYZ” using α-Fe2O3 (a=b =5.038 Å, c S/RGO compared to the standard Raman spectrum of Fe2O3 suggests
=13.776 Å) and SnO2 (a = b =4.73 Å, c =3.18 Å) as the starting model. an interaction between Fe2O3 and RGO [31]. The SnO2 nanorod peak
The spherical harmonics model [26,27] was applied to better model the was assigned as 697 cm−1 [32]. The spectra were dominated by carbon
peak intensity because both phases exhibited several preferred orienta- resonances at approximately 1597 (G band) and 1339 cm−1 (D band),
tion directions. The spherical harmonics model uses the general axis which correspond to sp2-hybridized carbon atoms in RGO and disorder
equation, as described by Bunge et al.[28] The preferred orientation in the sp2 carbon atoms, respectively. The ID/IG ratio (1.0) of the RGO
correction Op (h,y) for this formulation depends on both the reflection sheets in FNT/S/RGO was calculated using the difference Raman
h and the sample orientation y as follows: spectrum (Fig. S6), where ID indicates the nucleation site during the
NL L L formation of FNT/S nanostructures.
4П Various carbon weight ratios (wt%) of the FNT/S/RGO were
Op (h , y) = 1 + ∑ ∑ ∑ CLmn kLm (h ) kLn ( y)
L =2
2L +1 m =− L n =− L (1) calculated using STA analysis to maximize the electrochemical perfor-

Fig. 4. X-ray photoelectron spectra: (a) wide scan of FNT/S/RGO and narrow scan of (b) O 1 s, (c) C 1 s, (d) Sn 3d, and (e) Fe 2p spectra.

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mance, as shown in Fig. S7. The STA results for FNT/S/RGO in air 495.58 eV were attributed to Sn 3d5/2 and Sn 3d3/2 (Fig. 4d). In Fig. 4e,
were 27%, 34.9%, 39.8%, and 74.5%, as shown in Fig. S7a, b, c, and d, the peaks at 711.38 and 725.18 eV were assigned to Fe 2p3/2 and Fe
respectively. The small weight loss near 230 °C was induced by 2p1/2, respectively, which indicates the presence of Fe(III). The Sn3p3/2
adsorbed H2O molecules. The decomposition of RGO in FNT/S/RGO peak at approximately 716 eV provides further evidence of SnO2
was observed at approximately 470 °C. The weight percentage of FNT/ [33,35].
S/RGO was optimized by the presence of Fe2O3/SnO2 (~60.2 wt%) and
RGO (~39.8 wt%).
3.2. Electrochemical performance
The BET surface areas of FNT, FNT/S, and FNT/S/RGO were
revealed by the N2 adsorption/desorption isotherms collected at 77 K.
The electrochemical performance of the FNT, FNT/S, FNT/S/RGO
The BET specific areas for FNT, FNT/S, and FNT/S/RGO were
was investigated at 200 mA g‐1 and from 0.01 to 3.0 V, as shown in
8.39 m2 g‐1, 15 m2 g‐1, and 73 m2 g‐1, respectively, as shown in Fig.
Fig. 5a. The FNT exhibited an initial discharge capacity of
S8. Although the surface areas of FNT and FNT/S were lower than that
~793 mA h g‐1 (see Table S6). The capacity rapidly decreased with
of FNT/S/RGO, the FNT/S/RGO presented a substantially higher
increasing cycle number for the first 70 cycles, and the electrode
specific surface area because of the RGO. The substantially greater
maintained a capacity ~139 mA h g‐1 at the 220th cycle, showing a
surface area of the FNT/S/RGO specimen may improve the accom-
capacity retention of ~17% (Table S6). The FNT electrode exhibited
modation of Li ions and enhance the contact area between the electrode
unsatisfactory cycle performance because FNT exhibits low electrical
and the electrolyte during the electrochemical reaction.
conductivity during the insertion/extraction. However, the initial
The elemental compositions and oxidation states of the FNT/S/
capacity of FNT/S was ~1346 mA h g‐1 for the first cycle (retention of
RGO were further examined by XPS. The survey spectrum in Fig. 4
21% between the 1st and 220th cycles), which shows a more dramatic
reveals the co-existence of O, C, Sn, and Fe. The peaks in the O 1 s
decrease in capacity and even better cycle retention than the FNT
spectrum (Fig. 4b) at 530.48 and 532.09 eV were attributed to O2‐ and
electrode, as shown in Table S6. This initial capacity decay is attributed
C–O bonding, respectively [33]. Moreover, peaks of H2O (531.5 eV)
to the higher specific surface area and conversion reaction of FNT/S of
and OH−(533 eV) were not detected in the O 1 s spectrum, which
SnO2 nanorods. The FNT/S/RGO hybrid structure delivered a first
implies that FeOOH in the FNT/S/RGO was oxidized to Fe2O3,
discharge capacity of ~883 mA h g−1 (~1871 mA h g−1 at 0th cycle).
consistent with the XRD results [3,33]. The C1s XPS spectrum
The discharge capacity at the 220th cycle was ~795 mA h g−1, which
(Fig. 4c) reveals a dominant C–C (284.68 eV) peak in the graphene
corresponds to 90% retention between the 1st and 220th cycles, which
planes, which indicates the reduction of oxygen groups, and a C–O
is much higher than the retentions of both the FNT and FNT/S
peak at 285.88 eV [34]. The binding energies of Sn 3d at 487.08 and
specimens. Remarkably, the potential vs. specific capacity of FNT/S/

Fig. 5. Electrochemical characterization of FNT, FNT/S, and FNT/S/RGO: (a) cycle test between 0.01 and 3 V at a current density of 200 mA g−1; (b) alloying/dealloying curves of the
FNT/S/RGO at various cycles; (c) Coulombic efficiency of FNT, FNT/S, and FNT/S/RGO; (d) rate performance of FNT, FNT/S, and FNT/S/RGO at various current densities (200, 1300,
2150, 3020, 4320, and 200 mA g−1); (e) long-term cycle test of FNT/S/RGO at a current density of 1000 mA g−1 for 1000 cycles.

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RGO, as shown in Fig. 5b, exhibits excellent retention behavior from these results, FNT/S/RGO has the highest electrochemical perfor-
the 1st to 220th cycle. The coulombic efficiency (Fig. 5c) of FNT, FNT/ mance in terms of the cycle durability and high rate (4320 mA g−1)
S, and FNT/S/RGO at the 0th cycle was 76%, 77%, and 46%, in the cycle test. The long-term cyclability of the FNT/S/RGO electrode
respectively, which is attributed to electrolyte decomposition and SEI was investigated for 1000 cycles at a current density of 1000 mA g−1
formation on the electrode surface [36,37]. Although the lowest and is shown in Fig. 5e. The superior reversible capacity was
coulombic efficiency of FNT/S/RGO during the 0th cycle was a 854 mA h g−1 in the first cycle with a low capacity fade to
consequence of the high specific surface area induced by SEI, the 690 mA h g−1 after 1000 cycles. The superior cycle retention and rate
coulombic efficiency of FNT/S/RGO was progressively restored after capability of FNT/S/RGO is clearly attributable to the hybrid structure
the 13th cycle. of RGO, α‐Fe2O3, and SnO2, which is explained as follows: The RGO
The rate capability of FNT, FNT/S, and FNT/S/RGO as anodes was provides an enhanced conductive network and volume expansion
confirmed at various current densities (200, 1300, 2150, 3020, 4320, resistance as a consequence of its free space; Li ions have abundant
and 200 mA g−1), as shown in Fig. 5d. The rate capability of the FNT space because of the functional groups of RGO sheets; [38] and the Li
electrode showed poor performance: it substantially decreased from ions have a short diffusion path as a consequence of the SnO2 nanorod
200 mA g−1 in the 10th cycle to 4320 mA g−1 in the 50th cycle and α‐Fe2O3 nanotube structure.
(retention: 59%; 1st step – last step), as shown in Table S7. The To confirm the electrochemical reactions of FNT/S/RGO during Li
FNT/S electrode exhibited more stable rate capability than FNT and insertion/extraction, cyclic voltammetry (CV) was conducted at a scan
exhibited a capacity retention of 58.8% (1st step – last step). The FNT/ rate of 0.1 mV s−1 for 8 cycles. As shown in Fig. 6a, in the first cycle, α-
S/RGO electrode exhibited a much higher rate capability than FNT and Fe2O3 and SnO2 reacted with Li ions coexisted during the insertion/
FNT/S at all rate steps with better capacity retention (93.4%). From extraction. The cathodic peaks at 1.49, 0.88, and 0.6 V in the first cycle

Fig. 6. (a) Cyclic voltammograms of FNT/S/RGO at a scan rate of 0.1 mV s−1 for 8 cycles; (b) in situ EIS data for FNT/S/RGO from OCV (~2.6 V) to 0.01 V for 3 cycles; selected in situ
XRD patterns of FNT/S/RGO in the 2-theta range of (c) 3D plot of 25–27.5°, (d) top view of 25–27.5°, (e) 3D plot of 31.5–36.5°, and top view of 31.5–36.5°.

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are attributed to the sequential reaction of Fe3+ to Fe2+ and Fe°, step reversibly increased to 218 Ω. The Rtot of the 1st and 2nd cycles
respectively, in conjunction with SEI layer formation on the surface of also followed the electrochemical behavior of the 0th cycle. Finally, the
the active materials [36,39,40]. In the cathodic scan, the peak at 1.09 V Rtot of FNT/S/RGO decreased from 284 Ω in the 0th cycle to 145 Ω in
is assigned to the SnO2 reduction to Sn in conjunction with Li2O the 2nd cycle, which suggests that the electrical conductivity of FNT/S/
formation, as given in Eq. (5) [41]. The peak at approximately 0.014 V RGO was enhanced by the increase in Li-ion concentration in the
is attributed to the LiC6 reaction of RGO in Eq. (7) [42]. In the anodic electrode [44]. The steep slope of the Warburg tail during all cycles was
scan, the peaks of 0.60, 1.3, and 2.0 V are ascribed to the process of Li- kinetically assigned to rapid Li-ion diffusion from the electrolyte to the
ion extraction from the LixSn phase (Eq. (6)), [43] the reduction electrode surface.
reaction of SnO2 to Sn, and the oxidation of Fe° to Fe3+(Eq. (8)), To further examine the phase transition of FNT/S/RGO during the
respectively [36]. insertion/extraction, in situ XRD was conducted for 1 cycle in the
potential range from 0.01 to 3.0 V. The overall XRD pattern clearly
SnO2+4Li++4e−↔2Li2O+Sn (5)
indicates changes in the peak intensity, phase transitions, and mainly
the diffraction ranges 25–27.5° and 31.5–36.5°, as shown in Fig. 6c–f.
Sn+xLi++xe−↔LixSn (6) The diffraction peaks of SnO2 (110) at 26.5° gradually shifted to low
angles at 25.5° 2θ during the insertion process, which is related to the
C6 (RGO)+Li++e−↔LiC6 (7) lattice expansion according to the increasing Li concentration, as
shown in Fig. 6c and d. The XRD peak intensity of LiC12 at 25.5° 2θ
α-Fe2O3+6Li++6e-↔3Li2O+2Fe (8) (Fig. 6d) slightly increased during the extinction of the SnO2 (110)
peak, which might maximize the LiC12 reaction and recover to the
The charge/discharge characteristics of the FNT/S/RGO specimen previous intensity after the insertion process. In the case of the
exhibited good overlap in each cycle, which implies better capacity diffraction range from 31.5 to 36.5° 2θ, the diffraction peak of SnO2
retention with increasing number of cycles than the FNT and FNT/S (101) disappeared during the insertion process. However, the Sn (110)
specimens, as shown in Fig. S11. metal peak appeared, coinciding with the extinction of the SnO2 (101)
FNT/S/RGO was investigated with in situ EIS to define the peak, as shown in Fig. 6e and f. Hence, the SnO2 phase was converted
correlations between the electrochemical performance and the hybrid to the Sn metal phase during the insertion reaction in the 1st cycle.
structure of FNT/S/RGO during the insertion/extraction reaction. The These in situ XRD results show that the SnO2 conversion process
in situ EIS of FNT/S/RGO was measured from the open-circuit voltage during insertion/extraction can improve the electrical conductivity and
(OCV, ~2.6 V) to 0.01 V for 3 cycles. Figs. S12, S13, and S14 show the electrochemical performance, consistent with the in situ EIS results.
measured potentials on the voltage vs. capacity plot, Nyquist plots, and Ex situ TEM (Fig. 7a–g) after the cycling of FNT/S/RGO and
the total resistance (Rtot) values, respectively. The Rtot was 284 Ω at the elemental mapping (Figs. S9 and S10) was performed. The surface of
OCV of the 0th cycle and decreased to 125 Ω according to the insertion FNT/S at 1 V in the first cycle discharge became an amorphous phase,
of Li ions during the discharge step. Subsequently, Rtot in the charge

Fig. 7. (a) Schematic of the alloying/dealloying behavior of FNT/S/RGO; (b) ex situ TEM image of FNT/S/RGO after the first alloying step at 1 V; (c) enlarged image of boxed area from
(b); (d) schematic of FNT/S/RGO; (e) ex situ TEM image of FNT/S/RGO after 3 cycles; (f) schematic of the volume expansion of FNT/S/RGO being prevented during the alloying/
dealloying process; (g) schematic of the improved electrical conductivity of FNT/S/RGO after the conversion of SnO2 to Sn metal.

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Fig. 8. (a) Schematic of the in situ TEM of FNT/S/RGO encapsulated by two graphene sheets. FNT/S/RGO was immersed in the liquid electrolyte (LiPF6 in EC: DEC =50:50 vol). (b)–
(d) In situ TEM of FNT; (e)–(g) in situ TEM of FNT/S/RGO; (h)–(j) SEI layer observation of FNT/S/RGO.

and the insertion of Li ions into the FNT/S surface was confirmed, as intact and its surface was covered with Sn metal (Fig. 7e and elemental
shown in Fig. 7a, b and c. The elemental mapping image in Fig. 7b mapping image in Fig. S10), consistent with the in situ EIS and in situ
shows that FNT/S/RGO after the cycling test consisted of the carbon of XRD results.
RGO and the electrolyte, fluorine of LiPF6, oxygen of SnO2 and Fe2O3, The FNTs were also investigated using real-time in situ TEM
iron of the Fe2O3 nanotubes, and Sn of the SnO2 nanorods (Fig. S9). observations, as shown in Fig. 8a–j. Fig. 8a schematically illustrates
The charge/discharge mechanism of the multi-metal oxide electrode of the in situ TEM observations using a stack of two graphene cells, as
FNT/S/RGO confirms that the part of the SnO2 nanorod under greater reported elsewhere [20]. Although FNT exhibited a dynamic reaction
strain preferentially collapses with an increase in the amount of with Li (see supporting information for Movie 1), FNT exhibited good
inserted Li ions, which results in the strain distribution observed in resistance to volume expansion with increasing reaction time, as shown
the 3D Stephens model (Fig. 3b). After 3 cycles, FNT was structurally in Fig. 7e. The SnO2 nanorods in Fig. 8e–g was lithiated within 700 s;

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its crystal structure collapsed and was converted to an amorphous [7] G. Xia, N. Li, D. Li, R. Liu, C. Wang, Q. Li, X. Lü, J.S. Spendelow, J. Zhang, G. Wu,
ACS Appl. Mater. Interfaces 5 (2013) 8607–8614.
structure with increasing lithiation state (movie 2). This result is also [8] J.S. Chen, C.M. Li, W.W. Zhou, Q.Y. Yan, L.A. Archer, X.W. Lou, Nanoscale 1
consistent with the ex situ TEM results and the higher stress of SnO2 (2009) 280–285.
nanorods, as shown in the 3D Stephens model. The SnO2 nanorods [9] W. Zhou, C. Cheng, J. Liu, Y.Y. Tay, J. Jiang, X. Jia, J. Zhang, H. Gong, H.H. Hng,
T. Yu, H.J. Fan, Adv. Funct. Mater. 21 (2011) 2439–2445.
exhibit weak resistance to volume changes, which results in enhanced [10] S. Xu, C.M. Hessel, H. Ren, R. Yu, Q. Jin, M. Yang, H. Zhao, D. Wang, Energy
electrical conductivity as a sacrificial material, excellent cyclability and Environ. Sci. 7 (2014) 632–637.
high rate capability. The formation of an SEI layer on the FNT/S/RGO [11] W. Zhou, Y.Y. Tay, X. Jia, D.Y. Yau Wai, J. Jiang, H.H. Hoon, T. Yu, Nanoscale 4
(2012) 4459–4463.
surface, as shown in Fig. 8h–j (Movie 3), was much better than that on [12] D.T. Ngo, H.T.T. Le, C. Kim, J.-Y. Lee, J.G. Fisher, I.-D. Kim, C.-J. Park, Energy
FNT, which is related to the higher specific surface area and greater Environ. Sci. 8 (2015) 3577.
irreversible capacity of FNT/S/RGO, as shown in Fig. 5a. These results [13] D. Kong, H. He, Q. Song, B. Wang, W. Lv, Q.-H. Yang, L. Zhi, Energy Environ. Sci. 7
(2014) 3320–3325.
show that the initial irreversible capacity of the multi-metal oxide
[14] X. Liu, J. Zhang, W. Si, L. Xi, B. Eichler, C. Yan, O.G. Schmidt, ACS Nano 9 (2015)
electrode is associated with the irreversible phase conversion and strain 1198–1205.
distribution of the 3D Stephens model. [15] Y. Chen, X. Li, X. Zhou, H. Yao, H. Huang, Y.-W. Mai, L. Zhou, Energy Environ. Sci.
Supplementary material related to this article can be found online 7 (2014) 2689.
[16] S.J. Kim, S.-Y. Noh, A. Kargar, D. Wang, G.W. Graham, X. Pan, Chem. Commun. 50
at http://dx.doi.org/10.1016/j.nanoen.2016.12.058. (2014) 9932–9935.
[17] X.H. Liu, Y. Liu, A. Kushima, S. Zhang, T. Zhu, J. Li, J.Y. Huang, Adv. Energy
4. Conclusion Mater. 2 (2012) 722–741.
[18] M.T. McDowell, S. Woo Lee, C. Wang, Y. Cui, Nano Energy 1 (2012) 401–410.
[19] J.Y. Cheong, J.H. Chang, H.K. Seo, J.M. Yuk, J.W. Shin, J.Y. Lee, I.-D. Kim, Nano
Starting with an SnO2 nanorod array as the sacrificial material for Energy 25 (2016) 154–160.
the electrical conductivity, we successfully fabricated FNT/S/RGO an [20] J.M. Yuk, J. Park, P. Ercius, K. Kim, D.J. Hellebusch, M.F. Crommie, J.Y. Lee,
A. Zettl, A.P. Alivisatos, Science 336 (2012) 61–64.
anode via a microwave-assisted hydrothermal process without hard [21] K.S. Lee, S. Park, W. Lee, Y.S. Yoon, ACS Appl. Mater. Interfaces 8 (2016)
templating. The FNT/S/RGO exhibited substantially better electroche- 2027–2034.
mical properties than many SnO2/Fe2O3 nanostructured anodes, which [22] D.-F. Zhang, L.-D. Sun, C.-J. Jia, Z.-G. Yan, L.-P. You, C.-H. Yan, J. Am. Chem. Soc.
127 (2005) 13492–13493.
we attributed to the short diffusion distance and improved electrical
[23] D. Chen, L. Li, L. Guo, Nanotechnology 22 (2011) 325601.
conductivity resulting from the synergistic effect between SnO2 and [24] H. Rietveld, J. Appl. Crystallogr. 2 (1969) 65–71.
Fe2O3. Moreover, the RGO sheets have better electrical conductivity for [25] R.J. Hill, C.J. Howard, J. Appl. Crystallogr. 20 (1987) 467–474.
[26] M. Jarvinen, J. Appl. Crystallogr. 26 (1993) 525–531.
faster electrochemical kinetics and an elastic buffer effect to prevent the
[27] R. Von, J. Appl. Crystallogr. 30 (1997) 517–525.
expansion of SnO2 and Fe2O3 during the insertion/extraction reaction. [28] H.J. Bunge, Texture Analysis in Materials Science : Mathematical Methods, H.-J.
Consequently, this hybrid structure of FNT/S/RGO shows an out- Bunge,; translated by Peter R. Morris, Butterworths, London, Boston, 1982.
standingly long cycle life (690 mA h g−1 after 1000 cycles) at high rates [29] P. Stephens, J. Appl. Crystallogr. 32 (1999) 281–289.
[30] D.L.A. de Faria, S. Venâncio Silva, M.T. de Oliveira, J. Raman Spectrosc. 28 (1997)
(1000 mA g−1); it can also deliver a specific capacity of 795 mA h g−1 873–878.
after 220 cycles at 280 mA g−1 with good capacity retention (as high as [31] X. Teng, D. Black, N.J. Watkins, Y. Gao, H. Yang, Nano Lett. 3 (2003) 261–264.
90%). Moreover, the lithiation behavior and electrochemical enhance- [32] L. Shi, Y. Xu, Q. Li, Nanoscale 2 (2010) 2104–2108.
[33] Y. Luo, J. Luo, J. Jiang, W. Zhou, H. Yang, X. Qi, H. Zhang, H.J. Fan, D.Y.W. Yu,
ments of FNT/S/RGO were observed in various in situ analyses and in C.M. Li, T. Yu, Energy Environ. Sci. 5 (2012) 6559–6566.
the 3D strain distribution of the Stephens model. The highly functional [34] S. Stankovich, D.A. Dikin, R.D. Piner, K.A. Kohlhaas, A. Kleinhammes, Y. Jia,
3D nanostructures of the FNT/S/RGO composite are composed of Y. Wu, S.T. Nguyen, R.S. Ruoff, Carbon 45 (2007) 1558–1565.
[35] Y.Y. Fu, R.M. Wang, J. Xu, J. Chen, Y. Yan, A.V. Narlikar, H. Zhang, Chem. Phys.
naturally abundant materials, inexpensive, amenable to mass produc- Lett. 379 (2003) 373–379.
tion, and exhibit a high energy density, which should impart them with [36] G. Zhou, D.-W. Wang, P.-X. Hou, W. Li, N. Li, C. Liu, F. Li, H.-M. Cheng, J. Mater.
a wide range of applications in, for example, Li- and Na-ion batteries, Chem. 22 (2012) 17942–17946.
[37] P. Poizot, S. Laruelle, S. Grugeon, L. Dupont, J.M. Tarascon, Nature 407 (2000)
supercapacitors, photocatalysts, water-splitting catalysts, and gas sen- 496–499.
sors. [38] D. Pan, S. Wang, B. Zhao, M. Wu, H. Zhang, Y. Wang, Z. Jiao, Chem. Mater. 21
(2009) 3136–3142.
[39] Y. Zou, J. Kan, Y. Wang, J. Phys. Chem. C 115 (2011) 20747–20753.
Acknowledgements
[40] Y. Dong, K.C. Yung, R. Ma, X. Yang, Y.-S. Chui, J.-M. Lee, J.A. Zapien, Carbon 86
(2015) 310–317.
This study was supported by the National Strategic R & D Program [41] R. Li, X. Ren, F. Zhang, C. Du, J. Liu, Chem. Commun. 48 (2012) 5010–5012.
for Industrial Technology (10043868), which was funded by the [42] J. Yao, X. Shen, B. Wang, H. Liu, G. Wang, Electrochem. Commun. 11 (2009)
1849–1852.
Ministry of Trade, Industry and Energy (MOTIE). [43] X. Wang, X. Zhou, K. Yao, J. Zhang, Z. Liu, Carbon 49 (2011) 133–139.
[44] S. Yang, H. Song, X. Chen, Electrochem. Commun. 8 (2006) 137–142.
Appendix A. Supplementary material
Kangsoo Lee is currently a Ph.D. candidate in the
Supplementary data associated with this article can be found in the Department of Materials Science and Engineering at
online version at http://dx.doi.org/10.1016/j.nanoen.2016.12.058. Yonsei University, Seoul, Korea. His research is focused
on the fabrication and investigation of nanostructured and
thin film anode for high performance Li-ion batteries.
References

[1] Z.-S. Wu, G. Zhou, L.-C. Yin, W. Ren, F. Li, H.-M. Cheng, Nano Energy 1 (2012)
107–131.
[2] M.V. Reddy, G.V. Subba Rao, B.V.R. Chowdari, Chem. Rev. 113 (2013) 5364–5457.
[3] Y. Yang, X. Fan, G. Casillas, Z. Peng, G. Ruan, G. Wang, M.J. Yacaman, J.M. Tour,
ACS Nano 8 (2014) 3939–3946.
[4] Y.-M. Lin, P.R. Abel, A. Heller, C.B. Mullins, J. Phys. Chem. Lett. 2 (2011)
2885–2891.
[5] W. Zeng, F. Zheng, R. Li, Y. Zhan, Y. Li, J. Liu, Nanoscale 4 (2012) 2760–2765.
[6] J.B. Fei, Y. Cui, X.H. Yan, W. Qi, Y. Yang, K.W. Wang, Q. He, J.B. Li, Adv. Mater. 20
(2008) 452–456.

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Seoyoon Shin is now pursuing a master course in the Wooyoung Lee is a Professor of Department of Materials
Department of Nanoscience and Technology in Gachon Science and Engineering at Yonsei University in Korea. He
University, Gyonggi-Do, Korea. Her research interest received a BS and MS degree in metallurgical engineering
mainly focuses on the fabrication of solid state electrolyte from the Yonsei University. He received a Ph.D. degree in
for all solid state batteries. Physics from University of Cambridge, England. In recent
years, his research interests have centered on thermo-
electric materials and devices, various chemical sensors,
quantum transports in nano-devices and novel permanent
magnets.

Thomas Degen is currently working in the development Young Soo Yoon is Professor in Chemical Engineering at
department of PANalytical B.V., Almelo the Netherlands. Gachon University. His current research interests are (i)
He gained his Ph.D. working in the field of solid state all-solid Li-based secondary battery materials and systems,
chemistry at the Institute of Inorganic Chemistry, (ii) anode and cathode materials and systems for DMFCs,
University of Bonn, Germany. His research is mainly and (iii) process and device development based on two-
focused on algorithms and computing in the field of X- dimensional structures. He has expertise in the thin film
ray powder diffraction. process and measurement and synthesis of nanotailored
ceramic–metal composite powder for electrodes and solid
electrolytes of Li batteries and catalysts for fuel cells.

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