JOM

https://doi.org/10.1007/s11837-021-04717-8
 2021 The Minerals, Metals & Materials Society

NANOMATERIALS AND COMPOSITES FOR ENERGY CONVERSION AND STORAGE

Controlling Morphologies and Tuning the Properties of Co3O4

with Enhanced Lithium Storage Properties

YANHUA LU,1,2 JINHUI LI,1 CAINI ZHONG,1 ZHIFENG XU,1

WENJIN HUANG,3 JIAMING LIU,1,4 SHUBIAO XIA,3,5
and RUIXIANG WANG1,6

1.—Faculty of Materials Metallurgy and Chemistry, Jiangxi University of Science and

Technology, Ganzhou 341000, People’s Republic of China. 2.—Qingyuan Jiazhi New Materials
Research Institute Co. Ltd., Qingyuan 511517, People’s Republic of China. 3.—College of Chemistry
and Environmental Science, Qujing Normal University, Qujing 655011, People’s Republic of China.
4.—e-mail: [email protected]. 5.—e-mail: [email protected]. 6.—e-mail: [email protected]

Designing particles with a unique structure to accommodate volume varia-

tions on cycling is an effective strategy to improve the electrochemical per-
formance of metal oxide anode materials for lithium-ion batteries (LIBs).
Here, dandelion-like Co3O4 was prepared by a hydrothermal method following
heat treatment. In a similar preparation method, by adding a structural
modifier, i.e., sodium citrate, the dandelion-like Co3O4 could be transformed
into multi-shelled hollow Co3O4 microspheres. These two different Co3O4
morphologies show different electrochemical behaviors as anode materials for
LIBs. The multi-shelled hollow Co3O4 exhibited the better electrochemical
performance. At a current density of 200 mA g 1, the reversible capacity after
200 cycles reached 1132 mAh g 1. Even at a very high current density, i.e.,
1000 mA g 1, the reversible capacity was as high as 936 mAh g 1 after 300
cycles. Such an excellent electrochemical performance is mainly attributed to
the multi-shelled hollow structure that can alleviate the volume variation
during lithiation/delithiation; this further helps enhance the structural and
cycling stability. It also proves that the electrochemical performance of the
material can be enhanced by morphological modification.

variations during lithiation/delithiation, resulting

INTRODUCTION
in a faster capacity decay, thus limiting its
Lithium-ion batteries (LIBs) are widely used for application.3–5
applications such as notebook computers and mobile The morphology and structure of electrode mate-
phones, and also to power electric vehicles, thus rials have a significant influence on their electro-
showing broad applicability.1,2 At present, the the- chemical properties.6 Even the same electrode
oretical specific capacity of graphite for commercial material with a different morphology can have a
anode materials in LIBs is only 372 mAh g 1. It is notable impact on its electrochemistry,7–9 and this
crucial to develop anode materials with higher has prompted many researchers to tune the elec-
specific capacities to replace graphite to meet the trochemical performance by adjusting the morphol-
growing demand for higher energy densities. Among ogy and structure; for example, those materials with
various anode materials, metallic oxide materials, the following morphologies, such as nanorods,10,11
and especially Co3O4, is of great interest due to its nanotubes,12,13 nanofibers,14,15 nanosheets,16,17 and
high theoretical capacity, i.e., 890 mAh g 1. How- nanoparticles.18,19 Among these different morpholo-
ever, the Co3O4 anode material has large volume gies, multi-shelled hollow structured materials used
as LIB anodes generally show excellent electro-
chemical performances. The multi-shelled hollow
structure can: (1) increase the ratio of surface area
to volume to provide a more effective surface area,
(Received December 9, 2020; accepted April 26, 2021)
 Lu, Li, Zhong, Xu, Huang, Liu, Xia, and Wang

rich with active centers that increase specific capac- autoclave and reacted at 95C for 4 h. The different
ity; (2) provide enough room to alleviate the volume samples were centrifuged, washed with ultrapure
variation during lithiation/delithiation, and help water and ethanol, and then dried at 65C to obtain
enhance structural and cycling stability, and (3) the Co3O4 precursor. Finally, the Co3O4 precursor
prevent damage to the inner layer in the presence of was heated at 5C min 1 to 500C in air for 3 h. The
the outer layer and adjacent shell layers which can Co3O4 was formed as a black powder, and the
support each other, further improving cycling sta- samples were labeled as DL-Co3O4 and MSH-Co3O4,
bility.20–23 Metal oxides with a multi-shelled hollow in order of increasing sodium citrate concentration.
structure, such as Co3O4,20 NiO,21 and Fe2O3,23
exhibit excellent electrochemical performances as Structure and Morphological
LIB anodes. However, since most of these materials Characterization
are prepared by a template method, the preparation
The composition of the samples was characterized
process is relatively complicated and difficult to
by a Rigaku MiniFlex II x-ray diffractometer (XRD)
control; thus, it is not conducive for practical
with Cu Ka radiation (k = 1.54 nm). A scanning
applications.
electron microscope (SEM; MLA650F) and a trans-
Here, we have constructed a dandelion-like Co3O4
mission electron microscope (TEM; Tecnai G2 TF30
and multi-shelled hollow Co3O4 microspheres. The
S-Twin) were used to investigate the morphology
dandelion-like Co3O4 was prepared by a simple
and microstructure of the samples. X-ray photoelec-
hydrothermal method and pyrolysis, which was
tron spectroscopy (XPS) was performed using a
transformed into multi-shelled hollow Co3O4 micro-
ESCALAB 250. The sorption isotherms were
spheres by adding an appropriate amount of struc-
obtained using a Micrometrics ASAP 2020 analyzer
tural modifier, i.e., sodium citrate. Compared with
at 77 K.
the dandelion-like Co3O4, the multi-shelled hollow
Co3O4 microspheres exhibited better cycling stabil-
Electrochemical Characterization
ity. The multi-shelled hollow Co3O4 was prepared
without the use of any template. Since this prepa- A CR2016 button cell equipped with a lithium
ration method is facile and the process is easy to electrode as a counter electrode was used for the
control, it is a viable candidate for commercial electrochemical evaluation of the sample. A Celgard
applications. 2400 microporous polypropylene membrane was
used as the separator, and 1 M LiPF6 dissolved in
EXPERIMENTAL SECTION 1:1 dimethyl carbonate/ethylene carbonate was
used as the electrolyte. The polymeric binder, i.e.,
Syntheses of Samples
polyvinylidene fluoride, conductive carbon additive,
A schematic of the preparation of Co3O4 is shown i.e., super P, and the active material were taken
in Fig. 1. Typically, 2.9103 g of cobalt nitrate with a mass ratio of 1:2:7 and were mixed with N-
hexahydrate, 1.2016 g of urea, and two different methyl-2-pyrrolidinone. The slurry was subse-
amounts of sodium citrate (0 g and 0.5162 g) were quently pasted onto a copper foil and dried at
dissolved together in ultrapure water. The solution 120C to obtain the electrode. Galvanostatic tests of
was sealed into a Teflon-lined stainless-steel the assembled cells were performed on a LAND

Fig. 1. Schematic of the preparation of DL-Co3O4 and MSH-Co3O4.

Controlling Morphologies and Tuning the Properties of Co3O4 with Enhanced Lithium Storage
Properties

battery tester (BTI-40; China). A Metrohm Autolab (Fig. 2d), displays two peaks (530.1 eV and 531.6
PGSTAT302N (Netherlands) was used to perform eV), corresponding to lattice oxygen and surface
cyclic voltammetry (CV) measurements, with a scan oxygen of Co3O4, respectively.25
rate of 0.1 mV s 1 in the voltage range of 0.01–3.0 V The SEM and TEM were used to observe the
(versus Li/Li+). AC electrochemical impedance spec- morphological differences of the materials. The DL-
troscopy (EIS) was performed, with a frequency Co3O4 precursor had dandelion-like particle mor-
range of 0.01–105 Hz. phology (Fig. 3a), and the MSH-Co3O4 precursor
consisted of smooth spherical particles (Fig. 3b). As
a structural regulator, sodium citrate plays a crucial
RESULTS AND DISCUSSION role in changing the morphology of the precursor
The XRD patterns of DL-Co3O4 and MSH-Co3O4 particles. Citrate ions can easily adhere to the
(Fig. 2a), show no significant differences. The surface of the metal ions and change the crystal
diffraction peaks matches well with the standard growth direction.26 Thus, the dandelion-like micro-
Co3O4 (PDF #74-2120). The lack of impurity peaks spheres gradually become smooth surfaces, and the
indicates that the samples have high purity. XPS microspheres eventually form multi-shelled struc-
analysis was performed to study the composition of tures by self-assembly.27,28 As shown in the inset of
MSH-Co3O4, in which the XPS spectra (Fig. 2b) Fig. 3b, the MSH-Co3O4 precursor is composed of
demonstrate the existence of Co, O, and C. The multi-layers of spherical shells.
high-resolution XPS spectrum of Co 2p (Fig. 2c) The SEM images of DL-Co3O4 and MSH-Co3O4
presents two peaks (779.8 eV and 795 eV) and two are provided in Fig. 3c and d. The images show that
satellite peaks (788.7 eV and 804.4 eV), correspond- the overall morphology of the precursor particles in
ing to 2p3/2 and 2p1/2 of Co2+ and Co3+ of the Co3O4 the two samples is maintained, and the structure
phase.24 The high-resolution XPS spectrum of O 1s becomes relatively looser and more porous. The red

Fig. 2. (a) XRD patterns of DL-Co3O4 and MSH-Co3O4; XPS of MSH-Co3O4, (b) survey spectrum, (c) high-resolution spectra of Co 2p and (d) O
1s.
 Lu, Li, Zhong, Xu, Huang, Liu, Xia, and Wang

Fig. 3. SEM images of (a) DL-Co3O4 precursor, (b) MSH-Co3O4 precursor, (c) DL-Co3O4, (d) MSH-Co3O4.

Fig. 4. TEM images of (a, b) DL-Co3O4, (d, e) MSH-Co3O4; HRTEM image of (c) DL-Co3O4, (f) MSH-Co3O4.

dotted box in Fig. 3d shows that there are many further proves that MSH-Co3O4 has a multi-shelled
spherical shells and hollow spheres that are peeled hollow structure. This novel structure is formed
off due to the heat treatment. The inset of Fig. 3d mainly due to the heterogeneous shrinkage process
indicates that MSH-Co3O4 is regarded as a hollow caused by the imbalanced heat treatment of the
structure with a spherical shell inside. Figure 4d MSH-Co3O4 precursor microspheres during thermal
Controlling Morphologies and Tuning the Properties of Co3O4 with Enhanced Lithium Storage
Properties

decomposition.22,29 In addition, according to the Half cells were fabricated to explore the electro-
TEM images of DL-Co3O4 (Fig. 4a and b) and MSH- chemical reaction mechanism of the materials.
Co3O4 (Fig. 4d and e), the nanofibers in DL-Co3O4 Figure 6a and b show the CV curves of DL-Co3O4
and the multi-hollow shell of MSH-Co3O4 are com- and MSH-Co3O4, respectively. In the first cycle
posed of connected nanoparticles. Figure 4c and f discharge of DL-Co3O4 and MSH-Co3O4, a reduction
display the high-resolution TEM images of DL- peak appears at 0.89 V and 0.94 V, respectively,
Co3O4 and MSH-Co3O4, respectively, which clearly which is associated with the gradual reduction of
exhibit the d-spacing of 0.467 nm, corresponding to Co3O4 to Co (Co3O4 + 8Li+ fi 4Li2O + 3Co).32
the (111) plane of Co3O4. During the first charging cycle, the oxidation peaks
Furthermore, a nitrogen adsorption–desorption of DL-Co3O4 and MSH-Co3O4 are located at 2.08 V
test was performed of two samples (Fig. 5a and c). and 2.04 V, respectively, corresponding to the
The results show that the isothermal nitrogen process of Co being oxidized directly by Co3O4
adsorption–desorption curves of all the two samples (4Li2O + 3Co fi Co3O4 + 8Li+).33 In the subsequent
have clear hysteresis loops belonging to type-IV second cycle, the oxidation peaks and reduction
adsorption–desorption isotherms.30,31 The BET sur- peaks of DL-Co3O4 and MSH-Co3O4 are shifted,
face areas of DL-Co3O4 and MSH-Co3O4 are 91.54 which is mainly caused by electrochemical
m2 g 1 and 39.03 m2 g 1, respectively. Figure 5b polarization.34
and d show the pore size distribution curves, here Figure 6c and d display the charge–discharge
the average pore sizes of the two samples are seen to curves of DL-Co3O4 and MSH-Co3O4, respectively.
have decreased, i.e., for DL-Co3O4 and MSH-Co3O4, During the first discharge process, DL-Co3O4 and
the pore sizes are 21.25 nm and 16.91 nm, respec- MSH-Co3O4 have an obvious discharge plateau near
tively. According to the pore size distribution, the 1.15 V, corresponding to the formation of a solid
two samples have a mesoporous structure. electrolyte interphase (SEI) film and the

Fig. 5. Nitrogen isothermal adsorption-desorption curves of (a) DL-Co3O4, (c) MSH-Co3O4; pore size distribution curves of (b) DL-Co3O4, (d)
MSH-Co3O4.
 Lu, Li, Zhong, Xu, Huang, Liu, Xia, and Wang

Fig. 6. CV curves of (a) DL-Co3O4, (b) MSH-Co3O4; charge–discharge curves of (c) DL-Co3O4, (d) MSH-Co3O4.

decomposition of the electrolyte.35 During the material and the electrolyte; hence, the specific
charging process, the plateau that appears near capacity first increases and then gradually
2.09 V corresponds to the oxidation of Co and the decreases or stabilizes.37,38 The specific capacity of
decomposition of Li2O.36 The first cycle discharge DL-Co3O4 is shown to be initially higher than that
specific capacities of DL-Co3O4 and MSH-Co3O4 are of MSH-Co3O4; however, the specific capacity of
1046 mAh g 1 and 1221 mAh g 1, respectively, and MSH-Co3O4 exceeds that of DL-Co3O4 and the gap
the Coulombic efficiencies are 77.6% and 79.3%. The between the specific capacities gradually widens
initial loss of capacity is related to the formation of with the increase of the number of cycles. The
the SEI layer. At different numbers of cycles, the specific capacities of DL-Co3O4 and MSH-Co3O4 are
discharge capacity curve platform gradually became 345 mAh g 1 and 1132 mAh g 1, respectively, at
steeper as the specific capacity decreases, but the 200 mA g 1 after 200 cycles. At 1000 mA g 1, the
charge–discharge curve of MSH-Co3O4 had a better specific capacity of DL-Co3O4 is only 268 mAh g 1
overlap than that of DL-Co3O4, which indicated that after 300 cycles, while that of MSH-Co3O4 is main-
the electrochemical reaction stability of MSH-Co3O4 tained at 937 mAh g 1.
was better and that the polarization was lower. Figure 7b displays the rate performance of DL-
Figure 7a and e presents the cycling performance Co3O4 and MSH-Co3O4 at different current densi-
of DL-Co3O4 and MSH-Co3O4 at 200 mA g 1 and ties. The specific capacity of DL-Co3O4 is shown to
1000 mA g 1, respectively. Comparing them, we can be higher than that of MSH-Co3O4 at 100 mA g 1,
see that the overall trend of the two graphs is 200 mA g 1, 500 mA g 1, and 1000 mA g 1. As the
consistent. During the first cycles for DL-Co3O4 and current density is increased, the specific capacity of
MSH-Co3O4, a certain amount of capacity attenua- MSH-Co3O4 exceeds that of DL-Co3O4. Especially, it
tion occurs due to the formation of the SEI layer, can be seen that the cyclic stability of MSH-Co3O4 at
which can prevent direct contact between the active a high current density of 4000 mA g 1 is
Controlling Morphologies and Tuning the Properties of Co3O4 with Enhanced Lithium Storage
Properties

Fig. 7. (a) Cycle performance of DL-Co3O4 and MSH-Co3O4 at a current density of 200 mA g 1 along with coulombic efficiency of MSH-Co3O4;
(b) rate performance of DL-Co3O4 and MSH-Co3O4; (c) electrochemical impedance spectroscopy of DL-Co3O4 and MSH-Co3O4 after 50 cycles
and 100 cycles at 1000 mA g 1; (d) Rct values after fitting; (e) cycle performance of DL-Co3O4 and MSH-Co3O4 at a current density of 1000
mA g 1 and coulombic efficiency of MSH-Co3O4.

significantly better than that of DL-Co3O4. When area coupled with more active sites, and, therefore,
the density is restored from 4000 mA g 1 to 100 the specific capacity of DL-Co3O4 is greater than
mA g 1, the average specific capacity of MSH-Co3O4 that of MSH-Co3O4 in the initial stage of the cycle.
is higher than that of DL-Co3O4. However, the capacity of DL-Co3O4 decays rapidly
The electrochemical performance of DL-Co3O4 with the increase in the number of cycles, while
and MSH-Co3O4 exhibits a very large difference, MSH-Co3O4 can maintain stability, because its
which has a good relationship with their structure: structural stability is better than that of DL-
due to DL-Co3O4 having a larger specific surface Co3O4. MSH-Co3O4 has a multi-shelled hollow
 Lu, Li, Zhong, Xu, Huang, Liu, Xia, and Wang

structure, which can alleviate the volume variation To reveal the effect of DL-Co3O4 and MSH-Co3O4
during cycling, and this further helps enhance the on cycling stability, we disassembled the cells and
structural and cycling stability. investigated their morphologies. The SEM and TEM
Figure 7c shows the EIS of DL-Co3O4 and MSH- images of DL-Co3O4 and MSH-Co3O4 after 300
Co3O4 after 50 cycles and 100 cycles at 1000 mA g 1, cycles at 1000 mA g 1 are shown in Fig. 8. In sharp
respectively, and the charge transfer resistance contrast to DL-Co3O4, the structural stability of
(Rct) values after fitting are shown in Fig. 7d. After MSH-Co3O4 is better after cycling. It can be seen
50 cycles, the Rct value of DL-Co3O4 (28.6 X) is that the structure of DL-Co3O4 (Fig. 8a and c) is
smaller than that of MSH-Co3O4 (34.3 X), indicating completely collapsed, while MSH-Co3O4 (Fig. 8b and
that the charge transfer rate of DL-Co3O4 is faster d) can maintain the original structure. This is in
than that of MSH-Co3O4.39,40 However, after 100 accordance with the electrochemical tests, which
cycles, the Rct value of MSH-Co3O4 (35.6 X) is suggest that the cyclic stability of MSH-Co3O4 is
smaller than that of DL-Co3O4 (57.7 X), showing significantly better than DL-Co3O4.
that the charge transfer rate of MSH-Co3O4 is faster
than that of DL-Co3O4. In addition, according to the CONCLUSION
change range of the Rct values of DL-Co3O4 and
Dandelion-like Co3O4 was prepared by a
MSH-Co3O4, it can be explained that the charge
hydrothermal method and pyrolysis. Under the
transfer rate of DL-Co3O4 is significantly decreased
same conditions, by adding an appropriate amount
with the increase in the number of cycles, while the
of structural modifier, i.e., sodium citrate, dande-
charge transfer rate of MSH-Co3O4 is less affected
lion-like Co3O4 particles transformed into multi-
by the number of cycles. The results are consistent
shelled hollow Co3O4 microspheres. These two dif-
with the trends shown by the electrochemical
ferent Co3O4 morphologies exhibited significantly
performance.
different electrochemical behaviors as anode

Fig. 8. SEM images of (a) DL-Co3O4, (b) MSH-Co3O4, and TEM images of (c) DL-Co3O4, (d) MSH-Co3O4 after 300 cycles at 1000 mA g 1.
Controlling Morphologies and Tuning the Properties of Co3O4 with Enhanced Lithium Storage
Properties

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