Materials Letters 68 (2012) 28–31

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Materials Letters
journal homepage: www.elsevier.com/locate/matlet

Bubble template synthesis of copper sulfide hollow spheres and their applications in
lithium ion battery
Li Zhao, Fangqi Tao, Zhao Quan, Xianlong Zhou, Yuhong Yuan, Juncheng Hu ⁎
Key Laboratory of Catalysis and Materials Science of the State Ethnic Affairs Commission & Ministry of Education, South-Central University for Nationalities, Wuhan, 430074, PR China

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

Article history: A facile bubble template synthesis method has been developed to fabricate copper sulfide submicron hollow
Received 6 September 2011 sphere and porous sphere materials. Glutathione (GSH) was employed as bubble template source, sulfur
Accepted 29 September 2011 source and assembling reagent. The morphologies of hollow sphere and porous sphere can be obtained by
Available online 10 October 2011
varying the volume ratio of H2O/methanol in solvent system. The ratio of methanol is crucial in controlling
different morphologies possibly due to the difference in nucleophilic forces generated by O atoms of metha-
Keywords:
Porous materials
nol. When used as cathode materials in lithium ion battery, the obtained copper sulfide (CuS) hollow sphere
Hollow sphere samples show higher specific capacity than that of porous sphere.
Bubble template synthesis © 2011 Elsevier B.V. All rights reserved.
Nanocrystalline materials

1. Introduction transport length for Li + ions and electrons, therefore improving the
charge transfer and electron conduction of lithium ion batteries [19].
As a typical transitional metal chalcogenide, copper sulfide is a In this paper, we employed glutathione to serve as bubble source,
well known p-type semiconductor that has potential in applications sulfur source and assembling reagent. To the best of our knowledge,
of solar controller, solar radiation absorber and lithium ion batteries no reports have been made on the similar glutathione-assisted prep-
[1–4]. Considerable efforts have been made to investigate the synthe- aration of CuS hollow spheres.
sis of nano- and microstructure copper sulfide. Up to now, nanorods,
nanotubes, nanofibers, nanowhiskers, nanoflakes, nanowalls, nano-
2. Experimental section
cages, flowerlike, hollow spheres of copper sulfides have been suc-
cessfully fabricated [5–13]. Among these various morphologies,
2.1. Fabrication of CuS hollow spheres
hollow spheres with nano- or microsized dimensions gain extensive
attentions because of its prospective applications in catalysis, drug
In a typical procedure for the synthesis of copper sulfide hollow
delivery, light fillers, chemical storage and photonic crystals
spheres, 5.5 mmol Cu(NO3)2·3H2O was dissolved in 100 ml deionized
[14–16]. Fabrication of hollow sphere crystals has been conducted
water and 200 ml methanol, then 5.5 mmol GSH was added with con-
mainly by multistep hard template methods and soft template
stant stirring, forming a blue clear solution. After stirring for 30 min,
methods [17]. However, these methods involve the use of expensive
turbid whitish blue solution was obtained. The system was purged
and toxic organic reagents and need series of complicated procedures
with N2 for three times, then imposing a pressure of 15 bars Nitrogen.
requiring harsh reaction conditions. Bubble template is a good exam-
The autoclave was sealed and maintained at 160 °C for 24 h and then
ple of soft templates, enjoying the advantage of avoiding the template
cooled to room temperature naturally. The resulting products were
removal step.
filtered and washed for several times using deionized water and an-
Extensive studies have been carried out on the applications of
hydrous ethanol, dried at 60 °C for 12 h in air. For the formation of
nano- and microsized CuS in cathode materials in lithium ion batte-
porous spheres, the solvent system H2O/methanol with a volume
ries. Considering the high specific capacity of 561 mAh·g −1 and
ratio of 2:1 was employed while keeping other experimental param-
good electronic conductivity of 1 × 10 −3 Scm −1 [18], CuS is a promis-
eters unchanged in the typical procedure.
ing cathode material for the application in a low voltage battery sys-
tem. Moreover, the hollow sphere architecture largely reduces
3. Results and discussion

Fig. 1A shows the XRD patterns of the obtained hollow sphere and
⁎ Corresponding author. Tel.: + 86 27 67841302. porous sphere samples. The sharp diffraction peaks indicate that the
E-mail address: junchenghuhu@hotmail.com (J. Hu). samples are well-crystallized and can be indexed as hexagonal CuS,

0167-577X/$ – see front matter © 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.matlet.2011.09.108

A (107)
Relative intensity(a.u.)
(102)
(101) (103)
(006)
(100)
20 30
C D
Fig. 1. (A) X-ray diffraction patterns (a) CuS hollow spheres, (b) porous spheres. (B) TEM image of the as-prepared CuS hollow spheres. The inset is the corresponding HRTEM
image. (C) SEM image of the as-prepared CuS hollow spheres. The higher-magnification image is also inserted. (D) TEM image of the obtained CuS porous spheres.
well matching the standard values CuS (ICSD #61793, a = 3.796 Å,
c = 16.382 Å).
From the TEM image in Fig. 1B, the thickness and diameter are es-
timated to be 45 nm and 1.9 μm respectively. It should be noted that
several egg-like hollow spheres (highlighted with an arrow) are ob-
served, which further validates the bubble template mechanism.
The HRTEM image inserted in Fig. 1B reveals these nanoparticles' sin-
gle crystalline nature. The SEM image of a typical broken microsphere
in Fig. 1C indicates that the thickness of the shell is about 50 nm, con-
sistent with the conclusion of TEM measurement. The higher magni-
fication SEM image inserted in Fig. 1C reveals its detailed
nanostructure that samples are composed of aggregated nanoparti-
cles sizing between 4 and 10 nm. Moreover, CuS porous spheres can
be obtained by changing the volume ratio of H2O/methanol into 2:1.
The TEM image in Fig. 1D reveals the porous nature of the obtained
porous sphere sample.
Based on the above experimental results, the possible formation
mechanisms are anticipated to proceed according to Scheme 1. Func-
tional groups like −NH2, −COOH and −SH of GSH have a strong
tendency to interact with inorganic cations to form complexes, con-
firmed by Burford and co-workers [20]. Similarly, Cu2+ coordinates
with GSH to form initial precursor according to the model proposed in
Scheme 1(A) [21], which can be validated by the observations of turbid
whitish blue solution after the mixture being stirred for 30 min.
For the fabrication of hollow spheres, the solvent system H2O/
methanol with a volume ratio of 1:2 is employed. When the tempera-
ture rises, GSH ligands gradually hydrolyze into cysteine and other or-
ganic compounds. Cysteine ligands in the intermediate complexes B
are attacked by the strong nucleophilic O atoms of CH3OH molecules,
leading to the weakening and rupture of C\S bond [21,22]. The strong
nucleophilic force, resulting from a larger volume portion of methanol,
leads to relatively thorough rupture of C\S bonds and therefore the
L. Zhao et al. / Materials Letters 68 (2012) 28–31 29
B
(110)
(116)
(108) (203) (a)
(b)
40 50 60 70 80
2(degree) 1 µm 2 nm
1 µm
obtained S → Cu 2+ ← S nucleus bond with few ligands. Meanwhile,
Cu\O bonds rupture due to its comparatively low bonding energy.
The broken cysteine ligands produce gas bubbles of CO2 with the rup-
ture of −H2C\COOH. The produced CO2 bubbles consequently serve
as soft templates. To reduce the surface energy, the S → Cu 2+ ← S nucle-
us aggregate at the bubble surface, resulting in closely packed shell of
hollow spheres [23]. Then the metastable S → Cu 2+ ← S transform into
the stable state CuS. Moreover, the coexistence of several egg-like hol-
low spheres in Fig. 1B validates the bubble template mechanism.
Porous spheres are obtained by changing H2O/methanol ratio of
the solvent system into 2:1. For porous spheres, nucleophilic force is
relatively weaker due to the smaller ratio of methanol. Thus, C\S
bonds fail to rupture completely and the S → Cu 2+ ← S nucleuses are
bonded with more ligands. Obviously, the removal of these organic li-
gands with large volumes will lead to the porosity of the final CuS
spheres.
Fig. 2 shows the galvonostatic cycling of hollow CuS spheres in the
voltage rage of 0.05–3 V at a constant current density of 50 mA·g −1.
During the first discharge process, the hollow sphere samples show
an initial discharge capacity of 480 mAh·g −1, which amounts to 85%
of the theoretical value [18]. The porous sphere samples exhibit spe-
cific capacity of 276 mAh·g −1.
The first cycle cell behavior accords well with previously reported
papers [18,19,24]. Compared with porous spheres, hollow spheres
exhibit higher capacity, which possibly attribute to the relatively
stable structure. The hollow sphere architecture can accommodate
for volume expansion, supply more reaction sites on the surface and
reduce transport length for Li + ions as well as electrons, consequently
improving the charge transfer and electron conduction [19]. The
electrochemical behavior clearly reveals that CuS hollow spheres
have greater potential than porous spheres for lithium ion battery
applications.
30 L. Zhao et al. / Materials Letters 68 (2012) 28–31
Scheme 1. Schematic illustration of the formation of hollow and porous CuS spheres.
4. Conclusion
In summary, micro-sized copper sulfide hollow spheres and po-
rous spheres have been successfully fabricated by a one-pot bubble
template method in the presence of glutathione. The H2O/methanol
ratio of solvent system is observed to greatly influence the morphol-
ogy of the samples. When applied to lithium ion batteries, the as-
prepared CuS hollow spheres are more promising electrode materials
compared with porous spheres.
Acknowledgments
The Project was sponsored by the Scientific Research Foundation
for the Returned Overseas Chinese Scholars, State Education Ministry.
This work was also supported by National Natural Science Foundation
of China (20803096), NSF of Hubei Province (Distinguished Young In-
vestigator Grant 2010CDA082).
Fig. 2. First discharge curves of CuS (a) hollow spheres sample and (b) porous spheres
sample at constant current density of 50 mA·g−1.
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