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DOI: 10.1002/adma.200701364

Tin-Nanoparticles Encapsulated in Elastic Hollow Carbon Spheres

for High-Performance Anode Material in Lithium-Ion Batteries**
By Wei-Ming Zhang, Jin-Song Hu, Yu-Guo Guo, Shu-Fa Zheng, Liang-Shu Zhong,
Wei-Guo Song, and Li-Jun Wan*

Lithium batteries, as a main power source or back-up power capacity decay. Without appropriate structure design, the tin
source for mobile communication devices, portable electronic electrode typically fails after only a few discharge/charge
devices and the like, have attracted much attention in the cycles.[14,17] It is therefore very desirable to design a new tin-
scientific and industrial fields due to their high electromotive based materials mainly composed of metallic tin with high
force and high energy density. To meet the demand for batteries specific capacity as well as good cycle performance. Some
having higher energy density and improved cycle characteris- metal/oxides and carbon nanocomposites have been re-
tics, in recent years, a great deal of attempt has been made to ported[18–28] with high capacity and capacity retention when
develop new electrode materials or design new structures of used as anode materials, because the carbon shell has itself good
electrode materials.[1–10] For anode materials, among them, electronic conductivity and prevents the aggregation of active
some elementary substances such as silicon (Si), germanium materials, and especially thin carbon shell has good elasticity
(Ge), or tin (Sn) provide promising alternative to conventional to effectively accommodate the strain of volume change
carbonaceous anode active materials, because they are capable during Liþ insertion/extraction. Very recently, tin-encapsulat-
of alloying with more lithium and thus leading to the extreme ed spherical hollow carbon was synthesized by the pyrolysis of
high initial capacity density. For example, metallic tin has tin-containing organic precursors have exhibited higher capac-
recently been widely concerned as one of the promising ity and better cycle performance than unencapsulated mixture
anode materials for lithium batteries due to the following materials, in which the content of tin active substance was only
reasons.[11–14] Firstly, its theoretical specific capacity (Li4.4Sn, 24 wt %.[20] Nanostructured tin dispersed in a carbon matrix[29]
992 mA h g
1) is much higher than that of conventional graphite and carbon-encapsulated hollow tin nanopartides were also
(LiC6, 372 mA h g
1).[14,15] Secondly, the tin anode has higher reported as superior anode materials. These studies showed
operating voltage than graphite, so it is less reactive and that both coating tin nanomaterials with carbon layer and
the safety of batteries during rapid charge/discharge cycle could dispersing tin nanoparticles in carbon matrix are effective to
be improved.[14] Furthermore, a significant advantage of me- improve their electrochemical properties in lithium ion batter-
tallic tin over graphite is that it does not encounter solvent ies. It is obvious that the higher content of and smaller size of tin,
intercalation which causes irreversible charge losses at all.[14][16] as well as the thinner carbon coating will greatly contribute to
Unfortunately, the biggest challenge for employing metallic tin the further enhancement of material performance since the
as applicable active anode materials is that it is suffering from lithium storage density in tin is much higher than that in carbon.
huge volume variation during Liþ insertion/extraction cycle, Meanwhile, this tin-based anode material has to be designed to
which leads to pulverization of the electrode and very rapid own enough void volume to compensate the volume expansion
during Liþ insertion, which is important to improve its cycle
performance.
In the present work, we therefore designed a new approach to
[*] Prof. L.-J. Wan, W.-M. Zhang, Dr. J.-S. Hu, Prof. Y.-G. Guo,
S.-F. Zheng, L.-S. Zhong, Prof. W.-G. Song
synthesize tin nanoparticles encapsulated elastic hollow carbon
Beijing National Laboratory for Molecular Sciences spheres (TNHCs) with uniform size, in which multiple tin
Institute of Chemistry nanoparticles with a diameter of less than 100 nm were encap-
Chinese Academy of Sciences (CAS) sulated in one thin hollow carbon sphere with a thickness of only
Beijing 100080 (P.R. China)
E-mail: [email protected] about 20 nm, thus leading to both the content of Sn up to over
70% by weight and the void volume in carbon shell as high as
W.-M. Zhang, S.-F. Zheng, L.-S. Zhong about 70–80% by volume. This void volume and the elasticity of
Graduate School of CAS
Beijing 100080 (P.R. China)
thin carbon spherical shell efficiently accommodate the volume
change of tin nanoparticles due to the Li-Sn alloying-dealloying
[**] This work is supported by National Natural Science Foundation of reactions, and thus prevent the pulverization of electrode. As a
China (Grant Nos. 20603041, 20673121, 50730005,and 20575070), result, this type of tin-based nanocomposites have very high
National Key Project on Basic Research (Grant No. 2006CB806100),
and the Chinese Academy of Sciences. Supporting Information is specific capacity of >800 mA h g
1 in the initial 10 cycles, and
available online from Wiley InterScience or from the authors. >550 mA h g
1 after the 100th cycle, as well as excellent cycling

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In a typical experiment, the SiO2 spheres with a diameter of
about 400 nm were synthesized by classical St€ ober method and
used as templates in next step. Scanning electron microscopy
(SEM) image (not shown) shows the sample are uniform
spheres with a diameter of about 400 nm.[30] After hydrother-
mal hydrolysis of Na2SnO3  3H2O on the surface of these silica
spheres, a SnO2 shell can be deposited on SiO2 spheres.[31]
Figure 1a shows SEM micrograph of the obtained SiO2/SnO2
core–shell spheres. These spheres present the morphology
similar to SiO2 spheres with smooth surface and very few of
SnO2 small particles could be found in SEM view, indicating
that SnO2 may form a uniform shell coated on the surface of
SiO2 sphere template. Figure 1b shows the transmission elec-
Scheme 1. Synthetic scheme of tin nanoparticles encapsulated tron microscopy (TEM) image of the sample obtained after the
elastic hollow carbon spheres (TNHCs). silica cores were etched by a NaOH solution. The strong
contrast difference between the edge and the centre of these
spheres reveals that the sample consists entirely of hollow
spheres. These hollow spheres have uniform size and shell
performance, exhibiting a great potential as anode materials in thickness of about 25 nm and are composed of SnO2 nanopar-
lithium-ion batteries. ticles as confirmed by X-ray diffraction experiment described
TNHCs were prepared by in-situ reducing SnO2 hollow below. SnO2 hollow spheres were subsequently used as tem-
spheres with carbon coating. The synthetic procedure is de- plates to coat carbon shell on its outer surface by pyrolysis of
scribed in Scheme 1. In briefly, SiO2 spheres were firstly glucose at 190  C in an autoclave. After reaction and washing
synthesized according the St€ ober method[30] and used as tem- with water and ethanol, the white SnO2 hollow spheres turned
plates to prepare SnO2 hollow spheres. Next, polycrystalline into dark gray, indicating the carbon precursor layers were
SnO2 was deposited on SiO2 spheres to form uniform shells by formed by dehydration and polymerization of the glucose.[32]
the hydrolysis of Na2SnO3.[31] Then the SiO2 cores were etched SEM and TEM investigation on the sample (not shown), show it
by NaOH solutions to get hollow SnO2 spheres. After that, the still comprise similar uniform hollow spheres with thicker shell,
carbon precursor layers were coated on the outer surface of the demonstrating the SnO2/carbon double shell hollow spheres
hollow SnO2 spheres by the pyrolysis of glucose under hydro- were obtained. After heat-treatment at 700  C for 4 h under N2
thermal conditions.[32] Finally the product was dried and heat- atmosphere, the sample was turned into black completely,
treated at 700  C for 4 h under N2 atmosphere to carbonize the indicating the carbonization of the carbon precursor layers.
carbon precursor shell, and meanwhile the inner SnO2 shells The sample was further investigated by SEM and TEM.
were reduced to metallic tin by the carbon shells themselves to Figure 1c and d show the SEM and TEM micrographs, respec-
get the final TNHCs. tively. It can be seen that the morphology of the obtained
sample has greatly changed from uniform hollow spheres into
hollow spherical shell embedded with many nanoparticles. The
shells have an average diameter of about 500 nm and a thickness
of about 20 nm. The nanoparticles have diameters of about 60 to
100 nm. From the SEM image of an occasionally broken sphere
(inset in Fig. 1c) and the TEM image of integral spheres shown
in Figure 1d, it is obvious that these nanoparticles are studded
onto the inner surface of the hollow shells. These particles
appear as brighter spot in SEM image and as darker spot in
TEM image relative to outer shell, which implies that they may
make up of metallic substance. Large-scale SEM and TEM
images are shown in Figures S1 and S2, respectively, in Support-
ing Information.
To reveal the composition and structure of the above sam-
ples, powder X-ray diffraction (XRD) experiments were car-
ried out. Figure 2a shows XRD pattern of the sample shown in
Figure 1b, in which all diffraction peaks are in good agreement
with tetragonal rutile SnO2 (JCPDS No. 41-1445, S.G.: P42/
Figure 1. a) SEM image of SnO2 coated SiO2 spheres; b) TEM image of the
hollow SnO2 spheres; c) and d) SEM and TEM image of TNHCs, respec- mnm, a0 ¼ b0 ¼ 4.738 Å, c0 ¼ 3.187 Å), which confirms that the
tively. The inset in (c) is a close view of a single broken carbon spherical shell hollow spheres are constituted of tin dioxide and the silica core
studded with tin particles. have been removed completely. The highly broadened peaks

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Figure 4. Thermogravimetrics (TG) results of as synthesized and dried

SnO2/Carbon double shell hollow spheres under N2 atmosphere (a) and
TNHCs under synthetic air atmosphere (b). Both of the heating rates are
Figure 2. XRD patterns of hollow SnO2 spheres (a) and TNHCs (b). They 10  C min
1.
are identified as tetragonal rutile SnO2 (JCPDS No. 41-1445) and tetragonal
b-Sn (JCPDS No. 86-2265), respectively. The small peaks marked (*) belong
to orthorhombic SnO (JCPDS No. 24-1342), and the peaks marked (#)
belong to rutile SnO2 (JCPDS No. 41-1445).
embedded with several particles are clearly visible. It can be
verified the outer hollow spheres are carbon shells from CK
image (Fig. 3c) and the inner particles are tin particles from SnL
indicate that the SnO2 shells are composed of SnO2 crystallites image (Fig. 3d) in consistent with XRD result. In Figure 3c, the
with very small size. Figure 2b shows XRD pattern of the final CK signal is weaker in the center of the carbon shells, which is in
TNHCs. All intense peaks can be well indexed to b-Sn (JCPDS accordance with the hollow structure of the carbon spheres. On
No. 86-2265, S.G.: I41/amd, a0 ¼ b0 ¼ 5.831 Å, c0 ¼ 3.181 Å). the other hand, EDX spectrum analysis also tentatively pro-
The small peaks marked by * and # in Figure 2b can attribute to vides the result that the TNHCs contain 25 wt % carbon and
orthorhombic SnO (JCPDS No. 24-1342) and rutile SnO2 75 wt % tin.
(JCPDS No. 41-1445), respectively, which implies the metallic In further experiments, thermogravimetrics (TG) analyses
tin nanoparticles are slightly oxidized after exposed in ambient were carried out to display the conversion process from SnO2/
air during the preparation of sample. Carbon double shell hollow spheres into TNHCs. Figure 4a
In order to further determine the internal structure of the shows the TG result of as-synthesized and dried SnO2/Carbon
TNHCs, we carried out energy-dispersive X-ray (EDX) spec- double shell hollow spheres under N2 atmosphere. There are
trum and elemental mapping characterization of the TNHCs. four obvious valleys in DTG curve. The first one arises from the
Figure 3a shows the EDX spectrum of TNHCs. The peaks of C, loss of water, and the latter three ones originate from the
O, Si, and Sn are obviously identified. The strongest Si peak chemical reaction. It can be deduced that the carbon precursor
originates from Si wafer supporting the sample. The elemental spheres are carbonized at 380  C, and SnO2 shells partially react
maps further depict the internal structure of TNHCs. Figure 3b with carbon shells to produce SnO at 560  C, as confirmed by
shows normal SEM image of two TNHC spheres. The spheres XRD (not shown), and then further react with excessive carbon
at about 700  C, leading to metallic tin. Therefore, when SnO2/
Carbon double shell spheres were heated under N2 atmosphere
at 700  C, the following reaction took place:

SnO2 þ C ! SnðliquidÞ þ CO2 ðgasÞ ð1Þ

At this temperature, metallic tin is melted and have very low

vapor pressure. (See NIST Chemistry WebBook for details.) So
nearly no tin was lost during the heat treatment. The liquid tin
shrunk and formed tin nano-droplets due to surface tension and
adhered to the carbon shell. After cooling, tin nanoparticles in
solid form encapsulated in carbon shell were formed. On the
other hand, TG result of TNHCs under synthetic air atmo-
sphere was recorded to determine the chemical composition of
Figure 3. a) Energy-dispersive X-ray (EDX) spectrum of TNHCs. b) SEM
TNHCs, as shown in Figure 4b. The mass of sample kept
image of the TNHCs. c) and d) Elemental maps of C and Sn in TNHCs, unchanged below 200  C, which indicates that the sample was
respectively. quite stable under ambient atmosphere. When the temperature

1162 www.advmat.de ª 2008 WILEY-VCH Verlag GmbH & Co. KGaA,Weinheim Adv. Mater. 2008, 20, 1160–1165
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ties with respect to Li insertion/extraction. Figure 5a shows the
cycle voltammograms (CVs) of TNHCs. Four separated peaks
at 0.4–0.8 V on the positive-current side are related with the
extraction of Li from Sn and the broad background are related
with the extraction from carbon shells. The CV curves accord
with the bare Sn in literature.[15] These peaks originate from the
phase transitions between Sn, Li2Sn5, LiSn, Li7Sn3, Li5Sn2,
Li13Sn5, Li7Sn2, and Li4.4Sn, respectively. The TNHCs sample
was tested for lithium storage in the voltage window of 5 mV–3
V. The theoretical specific capacity of tin and carbon is 992 mA
h g
1 and 372 mA h g
1, respectively, so the TNHCs have a
theoretically calculated specific capacity of 831 mA h g
1.
Figure 5b shows the cycling performance of TNHCs. It has
specific capacity higher than 800 mAh g
1 in the initial 10 cycles
and higher than 550 mA h g
1 after the 100th cycle. It is
approximately 50% higher than the theoretical specific capacity
of currently used graphite even after the 100th cycle, which
amounts to 66.2% of its theoretical specific capacity (831 mA h
g
1). The initial capacity fading maybe partly ascribe to the little
pulverization of the inner tin particles, but the pulverization of
tin particles inside single carbon shells can not ruin the carbon
shells since there is enough void space to buffer the volume
expansion, so the capacity fading stopped after the 50th cycle.
This result is superior to the prior reported result of similar
materials synthesized by a modified resorcinol-formaldehyde
(RF) method,[20] in which carbon spheres have much thicker
Figure 5. a) The cycle voltammograms of TNHCs, the scan speed is 0.2 mV shells, the content of Sn is relatively low (about 24 wt %), and
s
1; b) The discharge/charge capacity profiles of TNHCs in 5 mV–3 V (vs. the specific capacity is about 400 mA h g
1. In addition, the
Liþ/Li) voltage window and C/5, the inset shows the first discharge/charge
present method can produce multiple particles in a single
profiles of TNHCs cycled at a rate of C/5.
carbon sphere (usually 5–10 particles), thus resulting in smaller
nanoparticles at the high content of tin. This new structure leads
to several advantages. First, the tin nanoparticles can alleviate
rose, the following reactions occurred:
the pulverization, and the particles are separated and do not
C þ O2 ! CO2 ðgasÞ ð2Þ aggregate together. Furthermore, all the nanoparticles adhere
to the inner surface of the carbon shell, which leads to larger
contact surface and better adherence. That is helpful for elec-
2Sn þ O2 ! 2SnO ð3Þ tron and lithium ion conduction. The peculiar structure mainly
contributes to the high performance. First, the hollow carbon
shell acts as a barrier to prevent the aggregation of tin nano-
Sn þ O2 ! SnO2 ð4Þ particles in different TNHCs. Second, the carbon shell is very
thin and the content of tin is high, which provides very high
weight capacity. Third, the hollow carbon shell provides a void
2SnO þ O2 ! 2SnO2 ð5Þ space. In the present work, the SiO2 spheres had a diameter of
about 400 nm, and the deposited SnO2 shells had a thickness of
25 nm, so the volume ratio of SnO2 to total volume inside the
Equation 2 resulted in a mass decrease while Equations 3–5 carbon shell is 0.3:1 in SnO2/Carbon double shell spheres. When
resulted into an increase, so the TG result exhibited a first mass the SnO2 shells were reduced to metallic tin, there would be
increase then decrease trend related with these actions. After 25% volume shrinkage, so the volume ratio of metallic tin to
the temperature rose to 800  C, the total reactions were Equa- total volume inside the carbon shell is 0.23:1 in the final TNHCs.
tions 2 and 4, and all carbon and tin in TNHCs had converted to The volume expansion factor of tin during Liþ insertion, namely
CO2 and SnO2, respectively. It can be accordingly determined from Sn to Li4.4Sn, is 3.59.[15] So, the Li4.4Sn occupies about 83%
that the TNHCs have a chemical composition of 26 wt % carbon of the total space in the hollow carbon spheres after 4.4 Li
and 74 wt % tin, which is consistent with the result of EDX insertion. The void space in TNHCs can right accommodate the
analysis. volume after expansion, which ensures the good cycle char-
In order to test the potential applicability of the TNHCs in acteristics as well as high volume energy density. The volume
lithium batteries, we investigated the electrochemical proper- expansion is also illustrated in Scheme 1. Finally, the TNHCs

Adv. Mater. 2008, 20, 1160–1165 ª 2008 WILEY-VCH Verlag GmbH & Co. KGaA,Weinheim www.advmat.de 1163
COMMUNICATION

are spherical in shape and uniform in size, which provides a high 190  C for 15 h. The dark gray products was harvested by centrifugation
and washed with DI water, then dried in an oven at 110  C.
packing density.[20]
Tin Nanoparticles Encapsulated Carbon Spheres: A 400 mg SnO2/
Furthermore, the entire synthesis procedure is simple and Carbon double shell spheres was heated in a quartz tube with an inner
easily to enlarged in this preparation. In addition, the diameter diameter of 7 mm at the rate of 6  C min
1 to 700  C in a 30 mL min
1 N2
of SiO2 spheres can be easily controlled by the St€ ober method, flow. The heating was continued for another 4 hours before the tube was
and the thickness of the SnO2 and carbon shell can be tuned as cool down to room temperature naturally.
Characterization: The products were characterized by scanning electron
well by simply adjusting the mole ratio of SiO2 spheres to microscopy (SEM, Hitachi S-4300F), transmission electron microscopy
Na2SnO3 and glucose, respectively. Therefore, we can control (TEM, JEM JEOL 2010), X-ray powder diffraction (XRD, Rigaku
the structure of the final products, including the diameter, Dmax-rB diffractometer with Cu Ka radiation, k ¼ 0.1542 nm, 40 kV,
thickness of the carbon shell, mass ratio of Sn/C, and volume 100 mA), thermogravimetrics(TG, Perkin-Elmer thermal analysis
equipment).
ratio of Sn/void space etc. Similar optimized TNHC structure
Electrochemical Characterization: Electrochemical experiments were
with smaller tin particles as well as high Sn content and appro- performed using Swagelok-type cells. The working electrodes were
priate void volume is expected to exhibit better cycle perfor- prepared by mixing the TNHCs, carbon black, and poly(vinyl difluor-
mance, since the smaller tin particles are the more effective on ide) (PVDF) at a weight ratio of 70:15:15, was pasted on pure Cu foil
the suppression of the pulverization is. The further investiga- (99.6%, Goodfellow). Glass fiber (GF/D) from Whatman was used as a
separator. The electrolyte consists of a solution of 1 M LiPF6 in ethylene
tion is under way in our group. carbonate (EC)/dimethyl carbonate (DMC) (1:1, in volume) obtained
In summary, a new approach has been designed to prepare tin from Ube Industries Ltd. Pure lithium foil (Aldrich) was used as counter
nanoparticles encapsulated elastic hollow carbon spheres electrode. The discharge and charge measurements were carried on an
(TNHCs, 74 wt % tin and 26 wt % carbon). The volume ratio Arbin MSTAT system. The cells were assembled in an argon-filled
of the tin nanoparticles and the void space encapsulated is about glove box. Cyclic voltammogram experiment was performed on a
Voltalab 80 electrochemical workstation at a scan rate of 0.2 mV s
1.
1:3, which can right accommodate the volume expansion during
Li-insertion. The high Sn content and appropriate void volume
render the electrode of TNHCs high specific capacity (>800 mA Received: June 06, 2007
h g
1 in the initial 10 cycles, and >550 mA h g
1 even after 100 Revised: September 28, 2007
Published online: February 27, 2008
cycles), high volume capacity and good cycle performance, and
hence make it a promising anode material for high-perfor-
mance lithium-ion batteries. Not only is this a further example
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Adv. Mater. 2008, 20, 1160–1165 ª 2008 WILEY-VCH Verlag GmbH & Co. KGaA,Weinheim www.advmat.de 1165