1. No category

Nano Research
Nano Res
DOI
10.1007/s12274-014-0648-z
Aerosol-Assisted Rapid Synthesis of SnS-Carbon
Composite Microspheres as Anode Material for Sodium
Ion Batteries
Seung Ho Choi1,2 and Yun Chan Kang1()
Nano Res., Just Accepted Manuscript • DOI: 10.1007/s12274-014-0648-z
http://www.thenanoresearch.com on November 24 2014
© Tsinghua University Press 2014
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1
TABLE OF CONTENTS (TOC)
Aerosol-Assisted Rapid Synthesis of SnS-Carbon
Composite Microspheres as Anode Material for
Sodium Ion Batteries
Seung Ho Choi1,2, Yun Chan Kang1,*
[1] Department of Materials Science and Engineering,
Korea University, Republic of Korea.
[2] Department of Chemical Engineering, Konkuk
University, Republic of Korea.
The formation mechanism of the hierarchical structured SnS-C
composite microsphere by one-pot aerosol process was investigated.
The carbon microspheres with uniformly attached cubic-like SnS
nanocrystals exhibited excellent Na-ion storage performances.
Address correspondence to First Yun Chan Kang, email; yckang@korea.ac.kr
Nano Research
DOI (automatically inserted by the publisher)
Research Article
Aerosol-Assisted Rapid Synthesis of SnS-Carbon
Composite Microspheres as Anode Material for Sodium
Ion Batteries
Seung Ho Choi1,2 and Yun Chan Kang1()
Received: day month year
ABSTRACT
Revised: day month year
SnS-C composite powders as anode material for Na-ion batteries were
prepared by one-pot spray pyrolysis. Carbon microspheres with uniformly
attached cubic-like SnS nanocrystals, which have an amorphous carbon
coating layer, were formed at a preparation temperature of 900 oC. The
initial discharge capacities of the bare SnS and SnS-C composite powders at
a current density of 500 mA g-1 were 695 and 740 mA h g-1, respectively. The
discharge capacities after 50 cycles and the capacity retentions measured
from the second cycle of the bare SnS and SnS-C composite powders were
25 and 433 mA h g-1, and 5 and 89%, respectively. The prepared SnS-C
composite powders with high reversible capacities and good cycle
performance can be used as sodium ion battery anode material.
Accepted: day month year
(automatically inserted by
the publisher)
© Tsinghua University Press
and Springer-Verlag Berlin
Heidelberg 2014
KEYWORDS
Tin sulfide • Anode
material
•
Carbon
Composite
• Sodium
Battery • Energy Storage
1. Introduction
Na-ion
batteries
possibly
the
particular, of most transition metal oxides in the
batteries
for
discharge process shift to lower values after the
large-scale energy storage. They can potentially
insertion of Na+ ions [9-17]. This shift, in turn,
replace lithium-ion batteries (LIBs) owing to the
hinders the attainment of sufficient electrochemical
natural abundance of Na resources [1-9]. NIBs
decomposition.
next-generation
of
(NIBs)
are
rechargeable
operate under a similar working principle as LIBs as
Sn-based materials, such as Sn metal, SnO2, SnS,
a result of analogous storage behavior in Na ions and
and SnS2, have been extensively studied as anode
Li ions [1-9]. Therefore, various types of materials
materials for LIBs and NIBs because of their high
which were developed for LIBs were also tested as
theoretical lithium-ion storage capacities [18-39].
the electrode materials for NIBs [10-17]. However, the
SnO2-based
successful use of these electrode materials in LIBs has
theoretical capacity of 894 mA h g-1 by forming the
not been replicated in NIBs. Cell potentials, in
Li15Sn4 alloy [18-24]. In the LIBs system, the plateau
Address correspondence to First Yun Chan Kang, email; yckang@korea.ac.kr
materials
can
deliver
a
reversible
Nano Res.
at approximately 0.8 V of SnO2 materials in their first
microspheres
discharge
sufficient
nanocrystals were prepared by a simple one-pot
electrochemical decomposition of SnO2 for the
spray pyrolysis process. The formation mechanism
lithium-ion storage process. However, SnO2 materials
and the Na-ion storage properties of the resulting
in
SnS-C composite powders were investigated.
process
NIBs
have
related
difficulty
to
attaining
sufficient
with
uniformly
attached
SnS
electrochemical decomposition because the cell
potentials of the metal oxide electrodes shift (about
2. Experimental
0.8 V) to lower values when lithium is substituted by
2.1 Synthesis of SnS-C composite powders.
sodium in conversion reactions [9]. In the first
SnS-C composite powders were prepared directly by
discharge step, SnS and SnS2 materials, unlike SnO2,
spray pyrolysis from the aqueous spray solution.
have higher initial plateau values (about 0.7 V) for
Figure S1 shows a schematic of the ultrasonic spray
electrochemical decomposition and are, therefore,
pyrolysis system that was used to prepare the SnS-C
promising candidates for use as Na-ion battery
composite. A 1,200 mm  50 mm (length  diameter)
anode materials [32-38]. However, SnS showed low
quartz reactor was used in the preparation. The
reversible capacities and poor cycle life, owing to
reactor temperature was maintained at 900 C and
larger Na-ion radius, slower reaction kinetics, and
the flow rate of the 10%-H2/Ar carrier gas was 5 L
huge volume expansion from Na-ion insertion.
min-1. An aqueous spray solution was prepared from
Sn-based nanomaterials of various structures have
tin oxalate (SnC2O4, Sigma-Aldrich) and thiourea
been studied in order to improve their capacities and
(CH4N2S, Junsei). Polyvinyl polyrridone (PVP) (Mw =
cycling performance for Na-ion storage [10,32-39].
45,000) was used as the carbon source material to
Sn-based carbon and graphene composite materials
form the carbon composite powders. 3.0 g of tin
have also been studied for Na-ion storage [32-39].
oxalate, 10 g of thiourea, and 3.5 g of PVP were
Inclusion of carbon materials improves the structural
dissolved in 250 mL of distilled water. Bare tin sulfide
stability of these Sn-based composites during cycling
powders were also prepared by one-pot spray
and augments the conductance of the active materials.
pyrolysis from the aqueous spray solution without
Tin sulfide-carbon composite materials prepared
PVP.
primarily by liquid solution methods exhibited good
electrochemical properties for Na-ion storage. Zhou
2.2 Characterizations
hybrid
The crystal structures of the powders were
nanostructured composites were found to have an
investigated by x-ray diffraction (XRD, X’pert PRO
excellent specific capacity of 492 mA h g after 250
MPD) using Cu K
cycles at a current density of 810 mA g [34]. Qu et al.
Morphological
reported that the SnS2-reduced graphene-oxide
using high-resolution scanning electron microscopy
hybrid
hydrothermal
(FE-SEM,
Na+
transmission electron microscopy (HR-TEM, JEOL
et
al.
reported
that
SnS-graphene
-1
-1
structures
processing
also
prepared
exhibit
by
excellent
storage
= 1.5418 Å ).
characteristics
Hitachi
S-4800)
were
and
investigated
high-resolution
JEM-2100F). An accelerating voltage of 200 kV was
properties [35].
Spray pyrolysis with a fast synthesis time has been
used in the case of HR-TEM. The specific surface
applied in the preparation of metal sulfide-C
areas of the microspheres were calculated from a
composite
Brunauer–Emmett–Teller (BET) analysis of nitrogen
microspheres
for
LIB
applications;
however, tin sulfide-carbon composite materials for
adsorption
Li- or Na-ion storage have not been prepared using
microspheres were also investigated using X-ray
this technique [40,41]. Therefore, in this study, carbon
photoelectron spectroscopy (XPS, ESCALAB-210)
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measurements
(TriStar
3000).
The
Nano Res.
with
Al
gravimetric
K
radiation
analysis
(1486.6
(TGA,
SDT
eV).
Thermal
Q600)
was
performed in air at a heating rate of 10°C min
−1
to
determine the amount of carbon in the microspheres.
2.3 Electrochemical Measurements
The capacities and cycle properties of the powders
were determined using a 2032-type coin cell. The
electrode was prepared from a mixture containing 70
wt% active material, 20 wt% Super P, and 10 wt%
sodium carboxymethyl cellulose (CMC) binder.
Stick-type
sodium
metal
and
microporous
polypropylene film were used as the counter
Figure 1. XRD patterns of the bare SnS and SnS-carbon
electrode and separator, respectively. The electrolyte
composite microspheres prepared by one-pot spray pyrolysis.
consisted of a solution of 1 M NaClO4 (Aldrich) in a
1:1 volume mixture of ethylene carbonate/dimethyl
structure with small impurity phases of SnO and
carbonate (EC/DMC) to which 5 wt% fluoroethylene
SnO2. However, the tin sulfide-carbon composite
carbonate (FEC) was added. The charge–discharge
powders prepared at 700 and 900 oC had phase pure
characteristics of the samples were determined by
orthorhombic SnS crystal structures. During spray
cycling the potential in the range of 0.001–3.0 V at
pyrolysis, tin oxide powder forms as an intermediate
fixed current densities. The corresponding cyclic
product of the decomposition of tin oxalate which
voltammetry (CV) was carried out at a scan rate of
occurs in the front part of the reactor that is
0.1 mV s . The dimensions of the negative electrode
maintained at 900 oC. In addition, the hydrogen
were 1 cm × 1 cm and the mass loading was
sulfide gas, formed by decomposition of thiourea,
approximately 1.2 mg cm . The capacities of this
enhances the reducing atmosphere induced by the
study were based on the total weight of SnS-C
10%-H2/Ar-reducing carrier gas surrounding the
composite. Electrochemical impedance spectroscopy
powders. Tin oxide is reduced to tin metal during
(EIS) was performed using a ZIVE SP1 over a
sulfidation of the powders in the rear part of the
frequency range of 0.01 Hz – 100 kHz.
reactor, resulting in the formation of tin sulfide. The
-1
-2
micron size and dense structure of the powders
3. Results and discussion
retard the reduction of tin oxide and sulfidation into
Bare tin sulfide and tin sulfide-carbon composite
tin sulfide. Therefore, the tin sulfide powders with
powders were prepared by one-pot spray pyrolysis
SnO and SnO2 impurities were prepared by one-pot
from the spray solutions with and without PVP as
spray pyrolysis from the spray solution without PVP.
the carbon source material. The crystal structures of
The tin oxide-carbon composite powder was formed
the powders are shown in Figure 1. As the XRD
as an intermediate product in the front part of the
pattern reveals, SnS powders prepared at 900 oC
reactor maintained at temperatures of 700 or 900 oC
without PVP had primarily an orthorhombic crystal
due to the decomposition of tin oxalate and
carbonization
of
PVP.
The
carbon
component
enhances the reducing atmosphere around the tin
oxide-carbon composite powders but also minimizes
the crystal growth of the tin oxide. Ultrafine tin oxide
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Nano Res.
powders, however, was changed by melting of SnS,
which has a melting temperature of 882 oC. Therefore,
rapid crystallization of the melted powder in the
outlet part of the reactor maintained at 900
resulted
in
the
plate-like
structure
o
C
observed.
Plate-like powders were also observed in the FE-SEM
and TEM images. Some powders consisted of stacked
structures of the nanoplates. These loosely stacked
nanoplates separated into several individual plates
during preparation of the bare SnS powders.
Elemental mapping images of the powders, shown in
Figure 2e, revealed that Sn is uniformly distributed in
the
powder.
However,
sulfur
and
oxygen
components were mainly located on the outside and
inside, respectively. In addition, a void was observed
in the elemental mapping images as shown by
arrows in Figure 2e. The melting of the tin oxide part
did not occur due to the incomplete sulfidation
Figure 2. Morphologies and elemental mapping images of the
bare SnS nanoplates prepared at temperatures of 900
oC:
process of the powder.
(a) and
(b) FE-SEM images, (c) and (d) TEM images, and (e) elemental
mapping images of Sn, S, and C components.
nanocrystals are uniformly dispersed within the tin
oxide-carbon composite powder. The ultrafine tin
oxide nanocrystals were rapidly reduced to tin
nanocrystals during the sulfidation process in the
rear part of the reactor. Therefore, SnS-C composite
powders with the phase pure crystal structure of
orthorhombic SnS were prepared by one-pot spray
pyrolysis even at a low preparation temperature of
700 oC. The powders were held for 6 s inside the
reactor that was maintained at this temperature.
The morphologies of the bare SnS powders with
SnO and SnO2 impurities are shown in Figure 2. The
SEM and TEM images showed the cubic-like
structure of the bare SnS powders. In general, one
spherical ceramic powder with a hollow or dense
structure was formed from each droplet in the spray
Figure 3. Morphologies and elemental mapping images of the
pyrolysis. In this study, one SnS powder was also
SnS-C microspheres prepared at 700 oC: (a) and (b) FE-SEM
formed from one droplet by the drying and
images, (c) and (d) TEM images, and (e) elemental mapping
sulfidation
images of Sn, S, and C components.
processes.
The
morphology of
the
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Nano Res.
shown in Figure 3. The nanoplates separated from
the spherical powder were also observed in the TEM
images shown in Figures 3c and 3d. Some of the
nanoplates which were loosely attached to the
surface of the spherical powders were removed
during ultrasonic vibration for the preparation of
TEM sample. Further characterization by elemental
mapping (Figure 3e) revealed that Sn and S are both
deficient in the surface layer whereas the carbon
component is uniformly distributed in the powder.
The TEM and elemental mapping images also
revealed that the ultrafine SnS nanocrystals are
uniformly distributed in the inner part of the
composite
powder.
nanoplates,
which
On
the
were
other
formed
hand,
SnS
during
the
sulfidation process, clustered the Sn component
around the surface of the powder. SnS-C composite
powders
Figure 4. Morphologies and elemental mapping images of the
oC:
prepared
at
900
o
C
had
different
morphologies compared to those produced at 700 oC.
(a) and (b) FE-SEM
Preparation at 900 oC resulted in the formation of
images, (c) and (d) TEM images, and (e) elemental mapping
cubic-like nanocrystals several tens of nanometers in
images of Sn, S, and C components.
size, which were uniformly attached to the spherical
SnS-C microspheres prepared at 900
powders (Figure 4). Elemental mapping revealed the
The morphologies of the SnS-C composite powders
with
the
of
spherical carbon powder (Figure 4e). Moreover,
orthorhombic SnS prepared at temperatures of 700
growth of the nanocrystals was initiated on the
and 900 oC are shown in Figures 3 and 4. The SnS-C
surface of the composite powder by consuming the
composite
structures
ultrafine SnS nanocrystals embedded within the
temperatures.
carbon sphere. In other words, Ostwald ripening
C resulted in powders with
resulted in uniform attachment of cubic-like SnS
spherical morphology decorated with nanoplates, as
nanocrystals, which have an amorphous carbon
irrespective
phase
pure
powders had
of
the
Preparation at 700
o
crystal
structure
attached SnS nanocrystals around the surface of the
hierarchical
preparation
Scheme 1. Schematic diagram of the detailed formation mechanism of the SnS-C microsphere in the one-pot spray pyrolysis.
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Nano Res.
observed
[42,43].
The
peak at 161.4 eV shown
in Fig. S3b can be indexed
as S2p of SnS [42,43]. The
C1s XPS peak observed at
284.6 eV in Figure S3c
was the binding energy
of the sp2 C–C bond of
amorphous
carbon
formed by carbonization
process of PVP.
The
electrochemical
properties of the bare SnS
and
SnS-C
composite
powders are shown in
Figure 5. Electrochemical properties of the SnS and SnS-C microspheres: (a) CV curves of SnS-C
prepared at 900 oC, (b) initial charge/discharge curves at a current density of 0.5 A g-1, (c) cycling
performances at a current density of 0.5 A g-1, and (d) rate performance of SnS-C prepared at 900 oC.
Figure
5.
The
voltammogram
curves
of
composite
the
cyclic
(CV)
SnS-C
powders
coating layer, to the carbon microspheres. The
prepared at 900 C from the first to the fifth cycles at
amorphous carbon layer around the cubic-like SnS
a scan rate of 0.1 mV s-1 in the potential range of
nanocrystals has a thickness of 5 nm (Figure 2d).
0.001–2.0 V are shown in Figure 5a. In the first
Scheme 1 shows a schematic of the detailed
discharge step, the distinctive reduction peak was
formation mechanism of the SnS-C composite
observed at around 0.7 V. This peak can be attributed
powder in the spray pyrolysis process.
to the conversion of SnS to Sn metal nanograins and
o
The thermogravimetric (TG) curves of the SnS-C
amorphous Na2S, and the formation of a solid
composite powders are shown in Figure S2. The TG
electrolyte interface (SEI) layer [33-38]. The broad
curves showed a distinct decrease in weight at
reduction peak below 0.7 V and the oxidation peaks
approximately 400 C owing to the decomposition of
observed at 0.28 and 0.72 V were ascribed to the
the carbon material. The carbon contents of the SnS-C
formation of NaxSn alloys and the multi-step
composite powders prepared at 700 and 900 C were
dealloying process of NaxSn to Sn metal, respectively
40 and 25%, respectively. The slight weight increase
[33-39]. The two oxidation peaks observed at 1.11 and
at around 370 C in the TG curve of the composite
1.31 V in the CV curves were ascribed to the
powders prepared at 900 C indicated the existence
reversible conversion reaction from Sn to SnS [33,34].
of small impurity of Sn metal. The BET surface areas
Figure 5b shows the initial charge and discharge
of the SnS-C composite powders prepared at 900 oC
curves of the powders at a current density of 500 mA
was 5 m2 g-1. To confirm the detail characteristics of
g-1. The bare SnS and SnS-C composite powders
the SnS-C composite powders prepared at 900 oC, the
prepared at 900 oC had long plateaus at around 0.7 V
XPS analysis of the powders was performed as
owing mainly to the conversion reaction of SnS to Sn
shown in Figure S3. Two strong Sn3d XPS peaks at
metal nanograins and amorphous Na2S [33-38].
around 486.7 and 495.1 eV, which can be attributed to
However, the SnS-C composite powders prepared at
Sn3d5/2 and Sn3d3/2 binding energies of SnS, were
700 oC had relatively short plateau at around 0.7 V
o
o
o
o
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Nano Res.
compared with those of the other two samples. The
4, and 5 A g-1, respectively. When the current density
unique structure of the SnS-C composite powders
was returned to 0.1 A g-1, the discharge capacity
prepared at 700 oC changed the shape of the initial
recovered to 540 mA h g-1.
discharge curve. The short plateau at around 0.7 V
Impedance spectra obtained both before and after
resulted from the conversion of the SnS nanoplates,
50 cycles from the bare SnS and SnS-C composite
which cover the carbon-SnS composite microsphere,
powders prepared at 900 oC are shown in Figure S5.
to Sn metal nanograins. However, the conversion
The Nyquist plots indicate compressed semicircles in
reaction of amorphous SnS located inside the SnS-C
the medium frequency range of each spectrum,
composite microsphere resulted in an inclined curve
which describe the charge transfer resistances (Rct)
in the voltage range of 0.5–0.01 V in the first
for these electrodes [44-46]. The bare SnS and SnS-C
discharging process. The distinct plateau resulting
composite powders had similar charge transfer
from the conversion reaction of SnS was not observed
resistances before cycling. Both samples exhibited a
in the second discharging process shown in Figure S4.
decrease in the resistances owing to the conversion of
The initial discharge capacities of the bare SnS and
crystalline SnS to amorphous-like SnS after cycling
SnS-C composite powders prepared at 900 C were
[47,48]. However, the SnS-C composite powders had
695 and 740 mA h g-1, respectively, and their initial
lower charge transfer resistance than that of the bare
Coulombic efficiencies were 72 and 63%, respectively.
SnS powders after 50 cycles. The SnS-C composite
In comparison, the SnS-C composite powders
powders with structural stability during cycling had
prepared at 700 oC had lower corresponding values
better cycling performance than that of the bare SnS
of 618 mA h g and 51%, respectively. These lower
powders.
o
-1
values, compared to those obtained in the materials
prepared at 900 oC, reflect the effect of a high content
4. Conclusions
of amorphous carbon with low capacity and high
In summary, the electrochemical properties of bare
initial
cycling
SnS and SnS-C composite powders prepared by
performances of the bare SnS and SnS-C composite
one-pot spray pyrolysis were compared. The bare
powders at a current density of 500 mA g-1 are shown
SnS powders had cubic-like or plate-like structures.
in Figure 5c. The SnS-C composite powders prepared
However, Ostwald ripening resulted in uniform
at 700 and 900 oC had good cycling performances.
attachment of cubic-like SnS nanocrystals, which
However, the discharge capacity of the bare SnS
have an amorphous carbon coating layer, to the
powders decreased after 10 cycles. The 50 discharge
carbon microspheres. The SnS-C composite powders
capacities and the corresponding capacity retentions
had higher initial capacities and better cycling
measured from the second cycle of the bare SnS and
performances than those of the bare SnS powders for
SnS-C composite powders prepared at 900 C were 25
Na-ion storage. The carbon content with low
and 433 mA h g and 5 and 89%, respectively. Figure
reversible capacities of the SnS-C composite powders
5d shows the rate performance of the SnS-C
prepared at 900 oC was ~25%. This value could be
composite powders prepared at 900 oC, in which the
easily controlled by changing the concentration of the
current density was increased step-wise from 0.1 to 5
PVP dissolved in the spray solution. In addition, the
A g-1 and returned to 0.1 A g-1. Ten cycles were
size of the SnS crystals which were attached to the
measured for each step in order to evaluate the rate
carbon
performance.
optimizing the preparation conditions such as the
irreversible
capacity
loss.
The
th
o
-1
exhibited 10
th
The
SnS-C
composite
powders
discharge capacities of 541, 455, 415,
microspheres
temperature,
could
residence
be
time,
controlled
by
and
reducing
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333, and 280 mA h g at current densities of 0.1, 1, 3,
-1
Nano Res.
atmosphere. The aforementioned findings confirm
Coming Precisely Engineered Colloidal Nanoparticles and
that SnS-C composite powders prepared by one-pot
Nanocrystals for Li-Ion and Na-Ion Batteries: Model Systems or
spray pyrolysis can be applied as an efficient anode
Practical
material for sodium ion batteries.
10.1021/cm5024508.
Solutions?
Chem.
Mater.
2014,
doi:
[7] Dahbi, M.; Yabuuchi, N.; Kubota, K.; Tokiwa, K.; Komaba, S.
Acknowledgements
Negative Electrodes for Na-Ion Batteries. Phys. Chem. Chem.
Phys. 2014, 16, 15007–15028.
This work was supported by the National Research
[8] Kim, Y.; Ha, K. H.; Oh, S. M.; Lee, K. T. High-Capacity
Foundation of Korea (NRF) grant funded by the
Anode Materials for Sodium-Ion Batteries. Chem. Eur. J. 2014,
Korea
20, 11980–11992.
government
(MEST)
(No.
2012R1A2A2A02046367).
[9] Klein, F.; Jache, B.; Bhide, A.; Adelhelm, P. Conversion
Reactions for Sodium-Ion Batteries. Phys. Chem. Chem. Phys.
Electronic Supplementary Material: Supplementary
2013, 15, 15876–15887.
material (Schematic diagram of spray pyrolysis
[10]
process,
photoelectron
Nanocomposites as Anode Materials for Na-Ion Batteries with
spectroscopy (XPS) spectra, second cycle profiles,
Superior Electrochemical Performance. Chem. Commun. 2013,
and electrochemical impedance spectroscopy (EIS) of
49, 3131–3133.
the bare SnS and SnS-carbon composite microspheres)
[11] Jian, Z.; Zhao, B.; Liu, P.; Li, F.; Zheng, M.; Chen, M.; Shi,
is available in the online version of this article at
Y.; Zhou, H. Fe2O3 Nanocrystals Anchored onto Graphene
http://dx.doi.org/10.1007/s12274-***-****-*
Nanosheets as the Anode Material for Low-Cost Sodium-Ion
(automatically inserted by the publisher).
Batteries. Chem. Commun. 2014, 50, 1215–1217.
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