Article

pubs.acs.org/cm

A Family of Mesocubes
Sai Karthik Addu, Jian Zhu, K. Y. Simon Ng, and Da Deng*
Department of Chemical Engineering and Materials Science, Wayne State University, 5050 Anthony Wayne Drive, Detroit, Michigan
48202, United States
S Supporting Information
*

ABSTRACT: It is challenging to develop a general universal procedure to fabricate mesoscale cubic structures on a large scale
with dierent nanoscale building units. It is always desirable to tune the chemical compositions within conned arrangements
without damaging the mesostructures to provide the desired physiochemical properties required by various devices/applications.
Herein, we report the successful design and facile preparation of a family of mesocubes with dierent compositions, including (a)
ZnSn(OH)6, (b) evenly distributed Zn2SnO4 and SnO2 nanoparticles, (c) hollow cubes of SnO2 nanoparticles, (d) high-ordered
nanoparticles of Zn2SnO4&Sn@C; (e) SnO2@C coreshell subunits, (f) SnO2@C nanoparticle aggregates enclosed with
oxidized carbon sheath, and (g) C nanobubbles, as building units, all, except ZnSn(OH)6, with the same conned arrangements
of nanoparticles as building units inside the same framework of cubic mesostructures. This family of mesocubes will provide a
rich pool of materials with dierent functional properties to meet demands in dierent applications and oer opportunities to
evaluate fundamentals of structurepropertyperformance relationships. On the basis of the best of our knowledge, this family
of facilely prepared mesocubes with unique combination of microsize cubes and compositions was reported for the rst time,
especially the carbon mesocubes formed by aggregation of carbon nanobubbles as the building subunits. Additionally, we
demonstrated, for the rst time, that two family members of mesocubes of Zn2SnO4&SnO2 and Zn2SnO4&Sn@C can be used as
anode materials in lithium ion batteries with impressive high packing densities and superior rate performance.

1. INTRODUCTION
The design and fabrication of nanoscale functional materials to
explore fundamentals of morphology-dependent properties and
numerous advanced applications of nanomaterials have been
attracting much attention in the past 2 decades. Nanoscale
materials are promising to achieve paradigm shifts in many
elds, such as catalysis,1 drug delivery,2 energy storage,35 solar
cells,6,7 absorption,8 photonics,9 chemical sensors,10 and
reactors in conned space on the nanoscale.11 The ability to
rationally design and facilely fabricate nanoscale materials will
enable the wide adoption of nanomaterials in many elds,
achieving tremendous positive impacts. Nanomaterials are
typically prepared by template-assisted methods with multiple
steps involved, hydrothermal methods under high temperature
and high pressure conditions, top-down ball-milling with high
energy, pyrolysis under high temperature, and chemical vapor
deposition. However, it is still challenging to develop a general
universal procedure to fabricate nanomaterials on a large scale
with the same conned arrangements on the mesoscale, but
2014 American Chemical Society

with dierent chemical compositions and properties to meet

demanding requirements of various applications.
Another challenging issue for nanoscale materials is the low
tapped density associated with the small particle size and large
surface area, which is not desirable for certain applications. For
example, nanomaterials have been extensively explored for
advanced lithium ion batteries to achieve high specic energy
(by mass), but the critical issue of energy density (by volume)
due to the low tapped density of nanomaterials is rarely
addressed. Low tapped density could prevent the production of
compact batteries, which is not acceptable for mobile electronic
devices and electric vehicles with limited space. In fact, the
tapped density of nanomaterials could be 1 order of magnitude
lower as compared to those in the bulk state. This critical issue
of low tapped density is most vividly illustrated by the following
Received: May 1, 2014
Revised: July 1, 2014
Published: July 8, 2014
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Figure 1. Schematic of the idea and procedure to prepare the family of mesocubes with dierent compositions and building substructures: (a)
mesocube of ZnSn(OH)6 as the starting family member; (b) cube of evenly distributed Zn2SnO4 and SnO2 nanoparticles obtained by annealing a;
(c) hollow cubes of SnO2 nanoparticles aggregates obtained by selective etching b in 1 M HCl; (d) cube of high-ordered nanoparticles of
Zn2SnO4&Sn@C aggregates obtained by CVD treatment of b under C2H2; (e) cube of SnO2@C coreshell subunits obtained by etching d in 2 M
HCl; (f) cube of SnO2@C nanoparticle aggregates enclosed with an oxidized carbon sheath obtained by oxidizing and etching d under concentrated
HNO3; and (g) cube with C nanobubbles as building units obtained by completely removing Zn and Sn elements in d with concentrated HCl.
Preparation of Mesocubes of Evenly Distributed Zn2SnO4
and SnO 2 Nanoparticle Aggregates. Mesocubes of
Zn2SnO4&SnO2 nanoparticle aggregates were prepared by calcinating
mesocubes of ZnSn(OH)6. To tune the size of the building units of
evenly distributed Zn2SnO4 and SnO2 nanoparticle, mesocubes of
ZnSn(OH)6 were calcinated at dierent temperatures of 650 and 800
C, at dierent ramping rates of 1 and 20 C/min, respectively.
Preparation of Hollow Mesocubes of SnO2 Nanoparticle
Aggregates. Typically, 50 mg of mesocubes of Zn2SnO4&SnO2
nanoparticle aggregates obtained with calcination at 650 C described
above were dispersed in 40 mL of 1.0 M HCl and kept for 24 h at
room temperature with stirring to etch o the Zn ions and core part of
the cube. The white product was collected by centrifugation, washed
with deionized water several times until the solution became neutral,
and then washed with ethanol and dried at 60 C.
Preparation of Mesocubes of High-Order Zn2SnO4&Sn@C.
Typically, the porous mesocubes of evenly distributed Zn2SnO4 and
SnO2 nanoparticle aggregates prepared by calcination at 800 C
described above were placed into a ceramic crucible and heated to 650
C in a quartz tube furnace with ramping rate of 20 C/min under Ar
ow. The chemical vapor deposition (CVD) process was carried out at
650 C for 1 h with a ow of 100 sccm of mixture gas (10% acetylene
with argon as the balance). The tube furnace was purged with argon
for at least 1 h to remove oxygen before CVD and cooled down
naturally under argon after CVD. SnO2 was reduced to metallic Sn by
acetylene under CVD conditions but not Zn2SnO4, and the black color
indicated a carbon coating.
Preparation of Mesocubes with SnO 2 @C CoreShell
Subunits. Typically, 25 mg of mesocubes of Zn2SnO4&Sn@C
obtained above was dispersed in 20 mL of 2 M HCl for 2 days to
selectively etch o Zn ions and metallic Sn. The as-treated sample still
black in color was collected by centrifugation, washed with deionized
water several times until the ltrate became neutral, and then washed
with ethanol.
Preparation of Solid Mesocubes of SnO2@Oxidized C
Sheath Nanoparticle Aggregates. Typically, concentrated nitric
acid (65 wt %, 15 M) was used to etch o Zn ions and oxidize metallic
Sn particles into SnO2 and oxidize the C sheath from the precursor
mesocubes of Zn2SnO4&Sn@C.
Preparation of Mesocubes of C Nanobubbles as Building
Units. The mesocubes of carbon were obtained by completely
removing Zn and Sn enclosed in the mesocubes of Zn2SnO4&Sn@C
by washing Zn2SnO4&Sn@C with concentrated HCl (12 M) etching
for 2 days. The black, acid-etched product was washed thoroughly and
collected.

example: the tapped density of graphite nanoparticles

(commercial) of 3040 nm in size is 0.26 g/cm3, as compared
to that of bulk graphite with density of 2.23 g/cm3, a dierence
of almost 9 times. Other issues associated with electrode
materials at the nanoscale are the poor electrical properties of
the electrode due to interparticle resistance and low Coulombic
eciency attributed to large surface area induced side reactions
between the electrode and electrolyte.
Here we reports a facile procedure to prepare a family of
cubic mesostructures of nanoparticle aggregates conned in
cubes on a large scale instead of simple random nanoparticles
to simultaneously overcome all the issues discussed above, in
particular, achieving electrode materials with high packing
density for lithium ion batteries. This family of cubic
mesostructures with various chemicals compositions and
building substructures, including (a) ZnSn(OH)6, (b) evenly
distributed Zn2SnO4 and SnO2 nanoparticles, (c) hollow cubes
of SnO2 nanoparticles, (d) high-ordered nanoparticles of
Zn2SnO4&Sn@C, (e) SnO2@C coreshell subunits, (f)
SnO2@C nanoparticle aggregates enclosed with oxidized
carbon sheath, and (g) cubes with C nanobubbles as building
units, will provide a rich pool of materials with dierent
chemical and physical properties to meet demands in dierent
applications. The overall idea and procedure with experimental
conditions involved in each step are illustrated in Figure 1. To
the best of our knowledge, family members cg above have
never been reported before. We also demonstrated, for the rst
time, that family members of b and d can be used as anode
materials in lithium ion batteries with very high packing density
with improve performances in lithium storage.

2. EXPERIMENTAL SECTION
Preparation of Mesocubes of ZnSn(OH)6. Mesocubes of
ZnSn(OH)6 as the starting family member was synthesized through
a room-temperature coprecipitation method. Typically, calculated
amounts of SnCl4 and ZnCl2 were dissolved in 50 mL of ethanol under
stirring, followed by the addition of 50 mL of an aqueous solution of
NaOH (0.32 M) drop-by-drop in 5 min. The mixture was stirred for 1
h and kept at room temperature without stirring for another 23 h. The
white precipitate was collected by centrifugation and washed with
ethanol and water several times to remove residual ions. The
ZnSn(OH)6 powder was dried in a conventional oven overnight.
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Materials Characterization. Powder X-ray diraction (XRD) was

carried out with a Rigaku Smartlab X-ray diractometer using Cu K
radiation ( = 0.154 18 nm). The morphologies of the products was
characterized by eld emission scanning electron microscopy (JSM7600 FE SEM, equipped with Pegasus Apex 2 integrated EDS, with
accelerating voltage of 15 kV) and by transmission electron
microscopy (JEOL 2010 TEM instrument, with accelerating voltage
of 200 kV).
Electrochemical Measurements. A homogeneous slurry was
prepared by mixing 80 wt % of the as-prepared active materials, 10 wt
% of conductivity enhancer (Super-P carbon black, Timcal), and 10 wt
% of polyvinylidene uoride (PVDF) binder in N-methylpyrrolidone
(NMP). The slurry was then applied to copper disks as current
collectors and dried in a vacuum oven at 80 C for 24 h. Coin-type
cells were assembled in an argon-lled glovebox using the coated
copper disk as the working electrode, metallic lithium foil as the
counter electrode, 1 M solution of LiPF6 in a mixture of ethylene
carbonate (EC) and diethyl carbonate (DEC) (1:1, v/v) as the
electrolyte, and PP/PE/PP trilayer membrane (Celgard 2320) as the
separator. The electrochemical cells were charged and discharged
galvanostatically at room temperature in the voltage window of 0.005
3 V on a MTI BST8-WA battery tester.

associated with metallic Sn appeared in Figure 2c after CVD

treatment, indicating the successful reduction of SnO2 to Sn by
acetylene under CVD conditions. The reduction of SnO2 to
metallic Sn under such a CVD condition is well-documented.1215
Mesocubes of ZnSn(OH)6. We identied zinc hydroxystannate [ZnSn(OH)6] as the starting family member for the
rich chemistry itself as well as its derivatives oered. Zinc
hydroxystannate can be easily prepared as cubic nanostructures
on a large scale.1619 Preparation of cubes about 100 nm in size
at room temperature has been reported by Li et al. from
Na2SnO33H2O and ZnCl220 and by Cao et al. by grinding.21
Hollow cubes around 500 nm were prepared by Wang et al.
through a room temperature alkali-assisted dissolution
process.19 Polyhedral microcrystals with coreshell structure
with size around 1 m were prepared by a room temperature
NH3 bubble templating method.22 The thermal decomposition
of ZnSn(OH)6 into Zn2SnO4 and SnO2 has been welldocumented.2326 Those derivatives from decomposed ZnSn(OH)6 not only oer dierent chemical and physical properties
but also can nd important applications in gas sensor and
lithium ion batteries. A size of around 1 m was the largest
among all the zinc hydroxystannate prepared at room
temperature, to the best of our knowledge. Here, we prepared
uniform ZnSn(OH)6 cubes with a size of 2 m without any
surfactants in the mixture of ethanol and water system at room
temperature for the rst time. We developed a simple
coprecipitation method with a water and ethanol mixture as
the solvent to provide the right conditions to generate large
amounts of mesocubes of ZnSn(OH)6 at room temperature.
The chemical composition was conrmed by XRD (Figure 2a).
The morphology of the as-prepred mesocubes of ZnSn(OH)6
is revealed by FESEM at dierent magnications in Figure 3a
c. All mesocubes of ZnSn(OH)6 are similar in size, as shown in
the low-magnication FESEM image (Figure 3a). The highmagnication FESEM image shows the perfect cubic structure
of ZnSn(OH)6, with at surfaces and sharp edges (Figure 3b,c),
and some nanoparticles adsorbed on the surface were observed.
The cubic structure and the solid nature of the mesocubes were
conrmed by TEM (inset of Figure 3a). The XRD (Figure 2a)
with sharp diraction peaks and the nearly perfect cubic
structure from TEM and SEM characterization (Figure S2 in
Supporting Information) all suggest that the meoscubes of
ZnSn(OH)6 are highly crystalline. The EDS of ZnSn(OH)6 is
shown in Figure 3d, and the atomic ratio of Zn:Sn is 1:1, as
expected.
Mesocubes of Distributed Zn2SnO4 and SnO2 Nanoparticle Aggregates. We successfully conned both Zn2SnO4
and SnO2 nanoparticles in mesocubes by simply calcinating
mesocubes of ZnSn(OH)6. Both Zn2SnO4 and SnO2 nanoparticles are highly functional, attracting much attention
recently. Zn2SnO4 nanoparticles can be used as transparent
conducting oxide,27 in gas sensors,28 in conductive inks in inkjet
printing,29 in dye-sensitized solar cells (DSSCs),26 and as anode
materials in lithium ion batteries.3032 Zn2SnO4 nanostructures
were typically prepared by complex and energy intensive
methods of hydrothermal, microwave-assisted hydrothermal
and vapor transport approaches.18,25,29,33 On the other hand,
SnO2 is a well-known wide band gap n-type semiconductor (3.6
eV). SnO2 nanostructures have been intensively explored to
enhance its performances in many applications, in particular,
gas sensors and lithium ion batteries.3437 The cubic structure
of the ZnSn(OH)6 precursor provides the template to generate

3. RESULTS AND DISCUSSIONS

Figure 2 shows the XRD patterns of three important family
members: (a) mesocubes of ZnSn(OH)6 as the starting

Figure 2. Selected representative XRD patterns of mesocubes to

conrm the compositions of (a) ZnSn(OH)6, (b) Zn2SnO4&SnO2
nanoparticle aggregates obtained by calcinating ZnSn(OH)6, and (c)
Zn2SnO4&Sn@C obtained by CVD treatment of Zn2SnO4&SnO2,
with all peaks assigned.

materials, (b) mesocubes of evenly distributed Zn2SnO4&SnO2

nanoparticles obtained by annealing ZnSn(OH)6 mesocubes,
and (c) mesocubes of high-ordered nanoparticles of
Zn2SnO4&Sn@C aggregates obtained by CVD treatment of
Zn2SnO4&SnO2 mesocubes. The XRD pattern of the starting
family member obtained by coprecipitation can be assigned to
primitive cubic ZnSn(OH)6 (JCPDS card no. 20-1455). No
other peak was observed, indicating the purity of as-prepared
ZnSn(OH)6 (Figure 2a). The XRD pattern of sample prepared
by calcinating ZnSn(OH)6 precursor at 800 C can be assigned
to Zn2SnO4 with cubic crystal structure (JCPDS card no. 241470) and tetragonal rutile SnO2 (JCPDS card no. 41-1445)
and no other peaks observed (Figure 2b). This XRD pattern
suggests the thorough conversion of ZnSn(OH)6 into Zn2SnO4
and SnO2 under heat treatment. After the CVD treatment
under acetylene, the composition of the products changed to a
mixture of Zn2SnO4 and tetragonal tin (JCPDS card no. 040673) (Figure 2c). The distinguishable peak at around 2 = 26
for SnO2(110) in Figure 2b disappeared in Figure 2c, and a
characteristic couple of peaks at around 2 = 30 and 32
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Figure 3. Mesocubes of ZnSn(OH)6: FESEM images at (a) low-magnication overall view showing a similar size distribution, and the inset shows a
typical mesocube viewed under TEM; (b) high-magnication zoomed-in view of a few mesocubes showing a rough surface; and (c) zoomed-in view
of a typical mesocube with the surface clearly revealed. (d) EDS of mesocubes of ZnSn(OH)6, and the atomic ratio of Zn:Sn is 1:1.

Figure 4. Mesocubes of distributed Zn2SnO4 and SnO2 nanoparticle aggregates. FESEM images of (a) low-magnication overall view showing the
perfect preservation of cubic structure after calcination treatment of its precursor of ZnSn(OH)6 and (b) high-magnifcaition zoomed-in view more
clearly showing the surface roughness and the aggregation of Zn2SnO4 and SnO2 nanoparticles and the porous nature. TEM images of (c) a single
mesocube with light contrast around the edges, suggesting porous structure, where dashed lines outline the orentiation of the mesocube and (d) the
zoomed-in view more clearly shows the aggregation of building nanounits. The samples were obtained by calcinating mesocubes of ZnSn(OH)6 at
800 C.
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Figure 5. Hollow mesocubes of SnO2 nanoparticle aggregates: SEM images of (a) low-magnication overall view showing the well-preserved
mesocubes and (b) high-magnication of a few typical mesocubes and the broken shell highlighted by arrows that reveals their hollow nature; TEM
images of (c) a few typical hollow mesocubes of SnO2 nanoparticle aggregates with clear contrast between the core and shell parts in each cube,
which further conrmed that they are hollow and (d) high-magnication zoomed-in view of a corner of the mesocube that clearly shows the
aggregation of SnO2 nanoparticles and shell thickness.

mesocubes can also be indirectly proved by the uniform

coating of carbon, the complete reduction of distributed SnO2
nanoparticles in mesocubes into Sn, and the successful
preparation of mesocubes of carbon bubbles, as will be
discussed. The EDS results of as-prepared Zn2SnO4&SnO2
are shown in Figure S1a (Supporting Information), with an
atomic ratio of Zn:Sn of 1:1. The atomic ratio of O (46.55
atom %) was decreased compared to the atomic ratio of O in
ZnSn(OH)6 (77.26 atom %) due to removal of the water
during the heating process and the conversion of ZnSn(OH)6
to Zn2SnO4 and SnO2.23,24,26,38
Hollow Mesocubes of SnO2 Nanoparticle Aggregates.
We successfully synthesized hollow mesocubes of SnO2
nanoparticle aggregates by selectively removing all Zn2+ ions
from the mesocubes of Zn2SnO4&SnO2 nanoparticle aggregates discussed above. The rational design was based on our
understanding that that Zn2+ ions can be easly etched o by
dilute hydrochloride acid.39 At the same time, SnO44 can be
protonated and dehydrated to SnO2, and SnO2 is relatively
stable, preserving the Sn. The possible reactions involved are

nanoparticles of Zn2SnO4 and SnO2 conned locally and

distributed evenly. The thermal decomposition reaction should
be26
2ZnSn(OH)6 Zn2SnO4 + SnO2 + 6H 2O

(1)

The morphology of the mesocubes of Zn 2 SnO 4 &SnO 2

nanoparticle aggregates was revealed by FESEM and TEM
(Figure 4). The low-magnication overall view shows that the
cubic structures were well-preserved after thermal decomposition (Figure 4a). More details of the structures were
revealed in the high-magnication FESEM image (Figure 4b).
The surface of the mesocubes of Zn 2 SnO 4 and SnO 2
nanoparticle aggregates is porous, indicating successful
conversion and formation of particle aggregates as compared
to its precursor of solid ZnSn(OH)6 mesocubes. The
mesocubes of mixed oxides were further characterized by
TEM (Figure 4c). The light contrast and course edges clearly
reveal those subunits of evenly distributed Zn2SnO4 and SnO2
nanoparticles. The high-magnication TEM image (Figure 4d)
more clearly shows the subunits and their aggregation. There
are evenly distributed nanoparticles in the size ranges of about
35 nm and 12 nm, which could be assigned to Zn2SnO4 and
SnO2 nanoparticles, respectively. The sizes measured from
high-magnication TEM agree with those estimated from XRD
(Figure 2b). The nanoparticle building units are randomly
distributed inside the mainframe of cubes, forming mesocubes
of nanoparticle aggregates. The void spaces between nanoparticle aggregations are observed. Those porous structures
could facilitate the diusion of acetylene during CVD through
the cubes on the nanoscale. The porosity through the

Zn2SnO4 + 4H+ 2Zn 2 + + H4SnO4

(2)

H4SnO4 SnO2 + 2H 2O

(3)
2+

Therefore, upon the complete removal of Zn ions, there

should still be SnO2 nanoparticles remaining in the framework.
The morphology of as-prepared hollow SnO2 mesocubes is
revealed by SEM and TEM (Figure 5). The cubic structure was
well-maintained, as revealed by low-magnication SEM (Figure
5a). It is interesting to note that the as obtained mesocubes of
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Figure 6. Mesocubes of high-order Zn2SnO4&Sn@C nanoparticle aggregates: FESEM images of (a) low-magnication overall view and (b) highmagnicaton top-view of two typical mesocubes; TEM images of (c) a typical mesocubes with light contrast around the edges, indicating preserved
porosity, and (d) high-magnicaton zoomed-in view more clearly showing the carbon sheath wrapping the Zn2SnO4&Sn nanoparticles. The
thickness of the carbon shell is 5 nm.

SnO2 are hollow. This is clearly revealed by the highmagnication view of a few typical mesocubes with broken
surfaces, and the holes highlighted by white arrows (Figure 5b).
Addtionally, we observed that the surface of mesocubes of
SnO2 was slightly deated (Figure 5b), which could be possibly
attributed to attack by acid etching, and that the void core
generated could not support the shell as compared to the solid
core before etching. The hollow structure was conrmed by
TEM (Figure 5c), with a clear contrast between the core and
the shell parts in each mesocube. The corner of a typical hollow
mesocube is shown in a zoomed-in TEM image, and the
thickness of the shell was about 280 nm (Figure 5d). The highmagnication image conrms the hollow nature of the
mesocubes and that the building units of the shell are SnO2
nanoparticle aggregates. The hollow mesocubes were entirely
formed by aggregated nanoparticles closely compacted, and
high-order random packing of nanoparticles creates nanopores
in the shell as well (Figure S3, Supporting Information). The
formation of unique hollow cubes, instead of porous solid
structures duplicated from its precursor of solid cubes, might be
ascribed as the following: During the preparation of mesocubes
of Zn2SnO4&SnO2 nanoparticle aggregates by heating ZnSn(OH)6, the heat was transferred from the shell to the core part
of the cubes and the diusion of water molecues in reversed in
direction. Thus, the Zn2SnO4&SnO2 nanoparticle formed on
the shell should have a larger grain size as compared to those
nanoparticle aggregates formed in the core part. In other words,
the smaller nanoparticles in the core part with larger surface
energy could be more easily attacked by acid etching as
compared to those bigger particles on the shell part.40

Otherwise stated, the shell will be more densely packed as

compared to the core part, forming hollow structures after
treatement. The complete removal of Zn2+ ions is conremd by
EDS analysis (Figure S1b, Supporting Information), where the
Sn peaks are dominant without any distinguishable Zn peaks, in
contrast to the EDS pattern of its precuror, Zn2SnO4&SnO2.
Mesocubes of High-Order Zn2SnO4&Sn@C Nanoparticle Aggregates. Another family member of mesocubes
of high-order Zn2SnO4&Sn@C were successfully prepared by
CVD treatment of the mesocubes of distributed Zn2SnO4 and
SnO2 nanoparticle aggregates as precursors. Here acetylene was
selected to play dual roles: (1) as reducing agent to selectively
reduce SnO2 to metallic Sn and (2) as carbon source to coat
Zn2SnO4&Sn with carbon sheaths. The reduction of SnO2 to
metallic Sn by acetylene is well-documented.14,15,41 The porous
3-D structures of precursor of mesocubes of distributed
Zn2SnO4 and SnO2 nanoparticle aggregates provide 3-D
channels for acetylene to diuse through the inside of each
cube and allows CVD to occur locally. In other words, the
carbon sheaths can encapsulate Zn2SnO4&Sn nanoparticles
through the cubes. The successful reduction of SnO2 to metallic
Sn by acetylene was conrmed by XRD (Figure 2c). The
results also suggest that Zn2SnO4 is highly stable under the
CVD conditions. The morphology of the Zn2SnO4&Sn@C
mesocubes was revealed by FESEM and TEM (Figure 6). The
uniform cubic structure was well-preserved after the CVD
process, as revealed by the low-magnication FESEM overall
view (Figure 6a). The zoomed-in view of two typical
mesocubes of Zn2SnO4&Sn@C (Figure 6b) reveals that there
are structures like bubbles/broken bubbles formed on the cube,
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Figure 7. Mesocubes of high-order Zn2SnO4&Sn@C nanoparticle aggregates analyzed by elemental mapping and EDS: (a) FESEM image of the
two mesocubes selected for elemental mapping, (be) the corresponding elemental mapping of C, O, Sn, and Zn, and (f) EDS analysis revealing
that the atomic ration Zn:Sn remains 1:1 as before CVD.

mesocubes of SnO2@C aggregates and carbon bubble

aggregates derived from this mesocubes of high-order
Zn2SnO4&Sn@C nanoparticle aggregates as discussed next
also conrmed that there are carbon sheaths throughout the
cube. Additionally, the EDS analysis shows that the atomic
ration of Zn:Sn remains 1:1, like its precursor (Figure 7f),
indicating there was no Sn loss during the CVD process,
although its melting point (less than 232 C) is signicantly
lower than the CVD temperature (650 C). This again suggest
that the carbon can completely encapsulate them. The carbon
content is 30.52 atom % from EDS analysis (Figure 7f).
Mesocubes with SnO2@C CoreShell Subunits. Mesocubes with SnO2@C rattlelike coreshell as building subunits
could be derived from mesocubes of Zn2SnO4&Sn@C by
etching with dilute HCl solution. This rational design was based
on our understanding that metallic Sn and Zn2+ ions can be
easily etched o in HCl solution, which is well-documented,
but carbon is stable. Meanwhile, it is understood that SnO44
can be protonated and dehydrated to SnO2 inside the carbon
under dilute HCl, forming SnO2@C coreshell particles. The
uniform cubic structure can be well-preserved after the acid
etching, as shown in the low-magnication FESEM image
(Figure 8a). The high-magnication FESEM in Figure 8b
shows more details about the nanosphere subunits at the corner

which conrmed the formation of carbon sheath. Additionally,

the porous structures remained with the surface still highly
rough, which indicates that the carbon coating occurred locally
on the nanoscale. Otherwise stated, mesoscale cubic structures
were well-preserved with high-ordered Zn2SnO4&Sn@C nanoparticles as building subunits. This is further conrmed by
TEM (Figure 6c). The light contrast around the edges and
rough edge lines all suggest its high porosity and the
aggregation of Zn2SnO4&Sn@C nanoparticles. This is further
conrmed by high-magnication TEM clearly showing the
details of the subunits (Figure 6d). The building subunits of
Zn2SnO4&Sn@C nanoparticles are wrapped by carbon sheaths
of about 5 nm in thickness or about 14 layers of graphenes
forming the carbon shell. The arrangement and order of the
aggregates were random, but there are visible layers of carbon
shell wrapping those Zn2SnO4&Sn nanoparticles. The void
between particles is lled with carbon. In other words, the
aggregation is more packed as compared to its precursor
(Figure S4, Supporting Information). Elemental mapping and
EDS analysis further conrmed the presence and even
distribution of elements (C, O, Sn, and Zn) in each mesocube
(Figure 7). The uniform distribution of carbon indicates that
the carbon formed throughout the whole cubes, not just on the
surface of cubes, as expected. Other family members of
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Figure 8. Mesocubes with SnO2@C coreshell subunits: FESEM images of (a) low-magnication overall view and (b) high-magnication cornerview of one typical mesocube; TEM images of (c) a typical mesocube with clear contrast between dark SnO2 nanoparticle and light carbon preserved
and (d) high-magnication zoomed-in view that clearly shows the SnO2@C coreshell nanoparticles as the building subunits and the space between
the dark SnO2 core and carbon shell; (e) FESEM image of the selected two mesocubes used for elemental mapping analysis and (f, g, and h)
corresponding elemental mapping results for C, O and Sn, respectively.

units was the same as its precursors due to the preservation of

carbon shells. As compared to its precursor of mesocube of
Zn2SnO4&Sn@C, the mesocube of SnO2@C is much lighter in
contrast under TEM through the cube, which suggests the
removal of Zn2+ ions and metallic Sn. The high-magnication

of the mesocube (in the area marked by a red dash in Figure

8a). The edges are light in contrast, indicating the partial
removal of core and that carbon bubbles remain at the edge and
on the surface. This is further conrmed by TEM (Figure 8c).
As expected, the overall aggregation of nanoparticle building
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Figure 9. Mesocubes of SnO2 nanoparticle aggregates enclosed by oxidized C sheaths: (a) low-magnication overall view and (b) high-magnication
view of a few typical mesocubes with highly rough surface; TEM images of (c) typical mesocubes with light contrast around the edges and a dark
body and (d) high-magnication zoomed-in view that clearly shows the SnO2 nanoparticle and oxidized or damaged C sheaths with holes.

case, highly concentrated HNO3 was used instead of dilute

HCl, to obtain more SnO2 and to oxidize and open the carbon
sheath. The EDS analysis of the mesocube of SnO2@oxidized
carbon nanoparticle aggregates showed a much higher content
of Sn (51.3 atom %) and lower content of carbon (40.1 atom
%) (Figure S1d,Supporting Information), as compared to the
EDS of dilute HCl treated SnO2@C sample (Figure S1c,
Supporting Information). Also, no peak for zinc can be
observed, indicating the full removal of Zn2+ ions. The uniform
cubic structure can be preserved after the treatment under
concentrated HNO3, as revealed by low-magnication FESEM
(Figure 9a). The high-magnication FESEM image of a few
typical treated mesocubes shows more details and surface
texture (Figure 9b). As compared to dilute HCl treated
mesocubes (Figure 8b), the mesocubes of SnO2@oxidized
carbon have coarse surfaces, which could be attributed to
oxidation of Sn and oxidization and opening of carbon
sheaths.40,42,44 The porous structure and aggregation of
nanoparticles of the mesocube were further characterized by
TEM (Figure 9c). As compared to the dilute HCl treated
sample of SnO2@C mesocubes (Figure 8c), the concentrated
HNO3 treated cube has more solid nanosubunits due to more
SnO2 being encapsulated, which was added through the
oxidization of metallic Sn into SnO2 by HNO3. A highmagnication TEM (Figure 9d) shows that the aggregated
nanoparticles encapsulated within severely damaged carbon
sheaths and holes were observed on the carbon sheaths.
Additionally, the thickness of the carbon sheaths was
signicantly reduced to about 3 nm as compared to that of
its precursor (Figure 6d). The mechanism of breaking and
thinning of carbon sheaths should be similar to shortening and
thinning of multiwalled carbon nanotubes by concentrated

TEM (Figure 8d) shows details about the SnO2@C coreshell

nanosphere subunits, and there are spaces between the SnO2
core and carbon bubbles, forming a rattlelike structure. There
are also carbon bubbles with the whole core part removed,
forming hollow carbon bubbles, which could be attributed to
the extract amount of HCl that can also remove SnO44 due to
the formation of H2[SnCl6]. The EDS mapping of SnO2@C
mesocubes in Figure 8eh demonstrates the uniformity of
carbon, oxygen, and tin on the mesocubes by the colors red,
green, and yellow, respectively. The EDS results (Figure S1c,
Supporting Information) show that carbon is dominant in the
composition, with atomic ratio of 90.26%, while a small amount
(3.72 atom %) of Sn element and O (6.03 atom %) exist in the
mesocubes.
Mesocubes of SnO2 Nanoparticle Aggregates Enclosed by Oxidized C Sheaths. Mesocubes of SnO 2
nanoparticle aggregates enclosed by oxidized C sheaths with
holes were derived from mesocubes of Zn2SnO4&Sn@C. The
rational design was based on our understanding that
concentrated HNO3, as a strong oxidant, can oxidize Sn back
to SnO2. The redox reaction between Sn and nitric acid can be
ascribed as42
Sn + 4HNO3(concd) SnO2 + 4NO2 +2H 2O

(4)

Note that metastannic acid (H2SnO3) may be generated as the

intermediate under highly concentrated HNO3 but could easily
dehydrate to form SnO2 during the drying process.43
Meanwhile, concentrated HNO3 has been widely used to
oxidize and functionalize carbon and open carbon nanotubes.
Under concentrated HNO3, amorphous carbon could form and
graphene layers could be cut open, providing additional
defective sites and increasing the carbon reactivity.44 In this
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Figure 10. Mesocubes of C nanobubbles: (a) low-magnication overall view and (b) high-magnication view of a few typical mesocubes; TEM
images of (c) a typical mesocubes of carbon nanobubbles as building subunits and (d) high-magnication zoom-in view clearly shows only carbon
bubbles as the building subunits and the complete removal of both Zn2SnO4 and Sn; (e) FESEM image of one selected mesocube used for elemental
mapping analysis and (f) the corresponding elemental carbon map.

HNO3.44 The opening of carbon sheaths could provide

additional reactivity sites for the SnO2 nanoparticles encapsulated, and this should be benecial to certain applications, e.g.,
sensors and photocatalysis.
Mesocubes of Carbon Nanobubbles. We also developed
the rst general procedure to produce mesocubes of carbon
nanobubbles using the mesocubes of Zn2SnO4&Sn@C as
precursor. This method, in principle, could be applied to
prepare carbon bubble aggregates in dierent geometries
starting from given ZnSn(OH)6 template with various shapes
instead of a cube, such as spheres or polyhedrons. Here, instead
of dilute HCl, concentrated HCl was used to completely
remove both Zn2SnO4 and Sn inside the precursor. We
understand that, under concentrated HCl, the H4 SnO 4
generated according to eq 2 will undergo the following
reaction:45,46
H4SnO4 + 6HCl H 2[SnCl 6] + 4H 2O

Therefore, both Zn and Sn can be completely removed from

mesocubes of Zn2SnO4&Sn@C, which left behind carbon only
under concentrated HCl. The as-prepared mesocubes of carbon
bubbles were characterized by FESEM and TEM (Figure 10).
The low-magnication FESEM shows that the all-cubic
structures were well-preserved after the acid etching in
concentrated HCl (Figure 10a). The high-magnication
FESEM image of a few typical carbon mesocubes indicates
that there was no collapse observed, with the cubic outlines
well-maintained. The good structure stability suggests that
there are carbon bubbles packed inside the cube to support the
structure. The complete removal of both Zn2SnO4 and Sn is
more clearly revealed by TEM (Figure 10c). Compared to the
mesocube of Zn2SnO4&Sn@C precursor (Figure 6c), the acidetched mesocube is much lighter in contrast under TEM, with
the size and shape well-preserved. The TEM image under high
magnication (Figure 10d) reveals some bubblelike hollow

(5)
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Figure 11. Electrochemical performances of mesocubes of Zn2SnO4&SnO2 and Zn2SnO4&Sn@C: (a) chargedischarge proles of the rst two
cycles of mesocubes of Zn2SnO4&SnO2; (b) corresponding dierential capacity proles (dQ/dV vs V) of part a; (c) chargedischarge proles of the
rst two cycles of mesocubes of Zn2SnO4&Sn@C; (d) corresponding dierential capacity proles (dQ/dV vs V) of part c; (e) cycling performances
of both mesocubes Zn2SnO4&SnO2 and Zn2SnO4&Sn@C at dierent currents of 50 and 100 mA/g.

transport into the mesocubes and deposited evenly through the

mesocubes.
Application of Mesocubes in LIBs with High Packing
Density. To demonstrate the tremendous potentials of this
family of mesocubes, we selected two members, mesocubes of
Zn2SnO4&SnO2 and Zn2SnO4&Sn@C, to evaluate in this
preliminary investigation, although all the members are
electrochemically active in reversible lithium storage and
other applications. Both nanoscale Zn2SnO4 and SnO2 have
been extensively explored as carbon-alternative anode materials
for lithium ion batteries (LIBs).18,39,4753 However, the
synergistic eect of evenly distributed Zn2SnO4 and SnO2
conned in a cube on reversible lithium storage has been
rarely studied. In our case, although the mesocubes are in
microscale, they are still electrochemically active, due to the fact
that the nanoparticles of Zn2SnO4&SnO2 as the building units
and the porous structure could facilitate the diusion of Li ions.
In other words, the salient advantages of nanoparticles, such as
short Li+ diusion paths and high rate performance, are not lost
even they are packed into mesocubes. Similarly, metallic Sn-

structures, which were the hollow carbon structures obtained

by removing the core of Zn2SnO4&Sn. The overall surface
distribution of the carbon bubbles is almost the same as its
precursor of mesocubes of high-order Zn2SnO4&Sn@C, and
the light contrast of the TEM image also suggests that the
wrapped cores of Zn2SnO4&Sn were almost completely
removed (Figure S5, Supporting Information). This observation again demonstrates that the carbon was uniformly coated
on all the subunits after CVD treatment, not just coated on the
outside surfaces of the mesocubes. EDS of the carbon
mesocubes (Figure S1e, Supporting Information) shows that
all the peaks associated with the elements of Sn and Zn are not
distinguishable. It is more evidence of the feasibility of this
method, and almost all of the Zn2SnO4 and Sn inside the
carbon was removed. The elemental mapping of the carbon
mesocube in Figure 10f reveals the uniform distribution of
carbon on the whole mesocube. The uniform coating of carbon
on all nanosubunits, even at the core part of the mesocubes, is
more evidence to demonstrate that the Zn2SnO4&SnO2
mesocubes were porous so that the acetylene vapor can
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based materials are also considered as an attractive lithiumstorage material, with a theoretical capacity of 990 mA h g1 (or
Li4.4Sn).54,55 However, Sn-based materials suer from poor
cyclability issues caused by volume changes during charging and
discharging. There are two main strategies to address the poor
cyclability issue: (1) to prepare materials on the nanoscale and
(2) to prepare Sn-based material/carbon composites. For
example, Zn2SnO4@C,18,31 SnO2@C, and Sn@C5559 have
demonstrated improved performance in LIBs. The encapsulating of Zn2SnO4&Sn in thin carbon sheaths and packing into a
cube on the mesoscale for lithium storage have not been
reported. Another issue associated with nanoscale materials
widely reported in literature is low tapped density, which makes
it dicult to improve the packing density of electrodes. Our
preliminary results show that both mesocubes of
Zn2SnO4&SnO2 and Zn2SnO4&Sn@C can be highly useful as
both high-energy and high-packing-density anode materials.
The results of preliminary investigation of the electrochemical performances of both mesocubes of Zn2SnO4&SnO2
and Zn2SnO4&Sn@C are summarized in Figure 11. In the rst
cycle discharge proles of both mesocubes of Zn2SnO4&SnO2
(Figure 11a) and Zn2SnO4&Sn@C (Figure 11c), plateaus
around 0.5 V (vs Li/Li+) are observed, which can be attributed
to the lithium insertion into Zn2SnO4 and subsequent
formation of alloy with Sn or Zn.32,60,61 This provide additional
electrochemical evidence of the presence of Zn2SnO4 in both
mesocubes. The rst cycle irreversible capacity losses (ICLs)
for mecosubes of Zn2SnO4&SnO2 and Zn2SnO4&Sn@C are
39.6% and 24.9%, respectively. This rst cycle ICLs can be
attributed to irreversible reduction of SnO2 and Zn2SnO4 and
formation of solid electrolyte interphase (SEI) in the former,
while only irreversible reduction of Zn2SnO4 and formation of
SEI in the later as SnO2 has been chemically reduced to metallic
Sn under CVD. The dierence in electrochemical reactions
involved in the two mesocubes could explain the dierence in
the rst cycle ICL observed. From the second cycle onward, the
chargedischarge proles are highly overlapped, indicating the
same electrochemical reactions. Given all the active materials
involved in the two mesocubes, the possible electrochemical
reactions are32,62
Zn2SnO4 + 8Li+ + 8e 2Zn + Sn + 4Li 2O

(6)

SnO2 + 4Li+ + 4e Sn + 2Li 2O

(7)

Sn + x Li+ + x e Sn + LixSn

(8)

Zn + y Li+ + ye Li yZn
6C + Li+ + e LiC6

(0 x 4.4)

(y 1)

Keeping in mind the dierent compositions of the two

mesocubes, unique peaks associated with SnO2 were observed
in mesocubes of Zn2SnO4&SnO2 (Figure 11b), and unique
peaks associated with metallic Sn and carbon sheaths were
observed in mesocubes of Zn2SnO4&Sn@C (Figure 11d). For
Zn2SnO4&SnO2, a stronger cathodic peak for SnO2 reduction
at about 0.85 V can be attributed to the reaction of SnO2 with
lithium ions and the formation of Sn and Li2O (Figure 11b),
according to eq 7, which was not observed in Zn2SnO4&Sn@C
(Figure 11d), indicating the presence and absence of SnO2 in
the former and latter, respectivlely, as expected. For
Zn2SnO4&Sn@C, the unique cathodic peak at about 0.6 V
could be assigned to the alloy of Li and Sn and the formation of
LixSn (Figure 11d), according to eq 8, while the oxidation
peaks between 0.4 and 0.8 V in the charging cycle could be
assigned to dealloying reactions of LixSn.14 Additionally, there
were no irreversible metallic Sn surface reaction peaks between
1.05 and 1.55 V observed in the rst discharge cycle, suggesting
that no metallic Sn was exposed to electrolyte, which provides
more evidence to show that all the metallic Sn was encapsulated
by carbon phase. In fact, the broad satellite peak around 0.9 V
could be assigned to the formation of SEI on the carbon surface
due to decomposition of electrolyte.
The capacity vs cycle number plots for the two mesocubes of
Zn2SnO4&SnO2 and Zn2SnO4&Sn@C are shown in Figure
11e. The specic capacities of 448 and 542 mAh/g were
obtained for mesocubes of Zn 2 SnO 4 &SnO 2 and
Zn2SnO4&Sn@C, respectively, after 20 cycles tested at a
current of 50 mA/g. When the currents were doubled to 100
mA/g, there was no noticeable fading in capacities observed
(392 and 512 mA h/g for Zn2SnO4&SnO2 and Zn2SnO4&Sn@
C, respectively), which indicates that the materials may have
good rate performance. Zn2SnO4&Sn@C even shows an
improved rate performance, for it only had very small fading
of 30 mA h/g, smaller than the fading of 56 mA h/g for
Zn2SnO4&SnO2 when charge/discharge currents were doubled.
After 35 cycles, capacities of 250 and 370 mA h g1 were still
maintained for mesocubes of Zn 2 SnO 4 &SnO 2 and
Zn2SnO4&Sn@C, respectively. Although the initial capacity of
the former is higher, the carbon coating could signicantly
improve the cycling performance of the latter. Carbon coating
could improve electrode conductivity and buer volume
variation, which are benecial to cycling performance.
It is particularly interesting to highlight that the mesocubes
of both Zn2SnO4&SnO2 and Zn2SnO4&Sn@C nanoparticle
aggregates have high tapped densities. Figure 12 illustrates the
volume occupied by the same weight of mesocubes as
compared to commercial TiO2 (AEROXIDE TiO2 P25). The
tapped densities for Zn2SnO4&SnO2 and Zn2SnO4&Sn@C
were estimated to be 1.14 and 0.98 g/cm3, respectively, which
are much higher than the tapped density of commercial TiO2 at
0.13 g/cm3. The signicant high tapped densities of both
mesocubes of Zn2SnO4&SnO2 and Zn2SnO4&Sn@C can be
attributed to close-compaction of cubic structures on the
mesoscale. High packing density is highly desirable to achieve
useful batteries and dramatically reduce the volume taken up by
battery systems for various applications. To illustrate the
signicance of high packing density, the capacity densities (by
volume) were estimated on the basis of specic capacities (by
mass). The specic capacities of mesocubes of Zn2SnO4&SnO2
and Zn2SnO4&Sn@C at the 35th cycle are 250 and 370 mA h
g1, and we assume that commercial TiO2 has a theoretical
specic capacity of 168 mA h g1. We nd the capacity densities

(9)
(10)

To better interpret the reactions involved in the two

mesocubes during the charge/discharge cycles, dierential
capacity proles (dQ/dV vs V) were plotted (Figure 11b,d).
For both mesocubes with the presence of the common
component Zn2SnO4, the cathodic peaks at about 0.45 and 0.14
V for the rst discharge processes are observed, which can be
attributed to eq 6 and forward eqs 8 9, respectively. The anodic
peaks at 0.6 and 1.34 V for the rst charge process can be
attributed to the backward eqs 8 and 9 and a partially reversible
reaction in eq 6. For the second cycle, the cathodic peak at 0.45
V disappeared and another dominant peak at 1 V was
observed, indicating dierent lithium insertion reactions.32,60,61
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concentrate HNO3 and concentrate HCl, respectively, and

EM images. This material is available free of charge via the
Internet at http://pubs.acs.org.

AUTHOR INFORMATION

Corresponding Author

*E-mail: da.deng@wayne.edu.
Author Contributions

S.A. and J.Z. contributed equally.

Notes

The authors declare no competing nancial interest.

ACKNOWLEDGMENTS
We thank the Lumigen Instrument Center, Wayne State
University, Detroit, MI.

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Figure 12. Optical image to compare the same weight of (a)

mesocubes of Zn2SnO4&SnO2 nanoparticle aggregates, (b) mesocubes
of Zn2SnO4&Sn@C nanoparticle aggregates, and (c) commercial TiO2
nanoparticles (AEROXIDE, P25). The tapped densities are estimated
to be 1.14, 0.98, and 0.13 g/cm3 for a, b, and c, respectively.

for mesocubes of Zn2SnO4&SnO2 and Zn2SnO4&Sn@C and

P25 TiO2 to be 285, 363, and 22 mA h cm3, respectively.
Otherwise stated, capacity densities could be about 13 and 17
times higher than that of commercial TiO2, even based on nonoptimized mesocubes.

4. CONCLUSIONS
In summary, we reports a facile procedure to prepare a family of
cubic mesostructures of nanoparticle aggregates conned in
cubes on a large scale to simultaneously overcome issues of
diculty in synthesis, tuning compositions, and properties, in
particular, achieving electrode materials with high packing
density for LIBs. This family of cubic mesostructures with
various chemical compositions and building substructures will
provide a rich pool of materials with dierent chemical and
physical properties to meet demands in dierent applications.
The chemical and physical properties of materials were tuned
by altering the compositions of the mesocubes while the same
cubic structures were preserved, ranging from semiconductors,
including Zn2SnO4 and SnO2, to conductive materials,
including Sn and carbon. The carbon mesocubes formed by
aggregation of carbon nanobubbles as the building subunits
were reported. We also demonstrated, for the rst time, that
two family members of mesocubes, Zn2SnO4&SnO2 and
Zn2SnO4&Sn@C, can be used as anode materials in lithium
ion batteries with very high packing densities. It is our ongoing
eort to explore applications for all members of this family of
mesocubes, and the results will be updated once available.

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ASSOCIATED CONTENT

S Supporting Information
*

EDS results of Zn2SnO4&SnO2 mesocubes, hollow SnO2

mesocubes, and mesocubes prepared from Zn2SnO4&Sn@C,
including SnO2@carbon, SnO2@ oxidized carbon and carbon
bubble aggregates, obtained by treated with dilute HCl,
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