Acta Metallurgica Sinica (English Letters) (2021) 34:383–389

https://doi.org/10.1007/s40195-020-01177-y

Hydrothermal Preparation of Homogeneous Cobalt Oxide

Nanomaterials as Stable Anodes for Superior Lithium Ion Batteries
Junke Ou1 · Shugen Wu2 · Hao Wang3

Received: 19 September 2020 / Revised: 4 November 2020 / Accepted: 19 November 2020 / Published online: 7 January 2021
© The Chinese Society for Metals (CSM) and Springer-Verlag GmbH Germany, part of Springer Nature 2021

Abstract
In this study, uniform Co3O4 nanoparticles are prepared via a simple and facile hydrothermal synthesis without calcination
treatment. When the Co3O4 nanomaterials are investigated as anodes for lithium ion batteries, a good electrochemical prop-
erty is achieved. Particularly, the reversible capacity of the as-synthesized Co3O4 nanoparticle has a significant growth from
383 mAh g−1 of the initial cycle to 471 mAh g−1 of the 300th cycle at 2 A g−1. Moreover, when it recovers to 50 mA g−1 after
different current densities, a superior reversible capacity of 695 mAh g−1 can be reached. Such favorable electrochemical
properties will make the as-obtained Co3O4 have a good application prospect as anode material for lithium ion batteries.

Keywords Co3O4 · Hydrothermal synthesis · Anode · Lithium ion batteries

1 Introduction available anode materials with superior electrochemical

performance [5, 6].
Nowadays, rechargeable Li-ion batteries (LIBs) have been Among various promising anode materials, cobalt oxide
universally applied in many portable electronic equipment (Co3O4), a member of transition metal oxides (TMOs), has
pieces and have attracted wide attentions to energy storage received extensive concerns in view of its large theoreti-
systems in electric vehicles (EVs) and hybrid electric vehi- cal capacity of about 890 mAhg−1 (2.4 times of commer-
cles (HEVs) due to the advantages of large energy density cial graphite anode) and stable chemical properties [7–9].
and excellent cycling property [1–4]. Unfortunately, the Unluckily, Co3O4 materials are still confronted with some
commercial graphite as anode shows a small theoretical tough drawbacks including low cycling stability and poor
capacity (372 mAh g−1), greatly restricting its further pop- rate performance, which are believed to be derived from
ularization in the high-power and high-energy devices. In inferior electronic conductivity and severe volume changes
order to meet the increasing requirements of LIBs, research- relevant to lithiation/delithiation processes [10, 11]. These
ers have been working on seeking for the replaceable and defects significantly hinder its practical applications in LIBs.
Aimed at handling the above-mentioned problems, the con-
struction of protective layer with carbonaceous component
is accounted as an appealing approach, which can improve
Available online at http://link.springer.com/journal/40195
the electrochemical properties of anode materials [12–14].
Supplementary Information The online version contains Nevertheless, the presence of carbonaceous materials can
supplementary material available at (https://doi.org/10.1007/ not only suppress the capacity of Co3O4 but also make the
s40195-020-01177-y). preparation process complex [15]. Hence, it is highly desir-
* Junke Ou able to design Co3O4 with suitable architectures to obtain
[email protected] high capacity and long-term cycling performance. At pre-
sent, nanostructured Co3O4 has been adopted as anode
1
Institute for Advanced Study, Chengdu University, materials for LIBs, such as nanosheets [16], nanowires [17],
Chengdu 610106, China
nanoplates [18], and nanocubes [19]. For instance, Gou et al.
2
Zhanglan Honors College, Chengdu University, synthesized Co3O4 plates and even at 1.6 A g−1, exhibit-
Chengdu 610106, China
ing the discharge capacity of 217.8 mAh g−1 [20]. Co3O4
3
School of Mechanical Engineering, Chengdu University, nanosheets showed excellent rate property with the charge
Chengdu 610106, China

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384 J. Ou et al.

capacity of 287 mAh g−1 at 1 A g−1 [21]. It is also striking improve the performance in the future study. To sum up,
to note that the strategies for the preparation of advanced the as-obtained Co3O4 nanoparticles are expected to make a
Co3O4 nanomaterials are usually complex and costly. There- great improvement in the development of nanomaterials for
fore, it is still a challenge to explore a facile fabrication for LIBs and realize large-scale production.
the pure Co3O4 anode materials with high properties.
Herein, in this study, we have successfully fabricated
unique Co3O4 nanoparticles with uniform size through a 2 Experimental
simple and facile hydrothermal method without undergoing
any calcination. Typically, the as-prepared Co3O4 nanopar- 2.1 Synthesis of Co3O4 Material
ticles possess good structural stability and favorable charge
transfer reaction for Li+ intercalation and deintercalation, As described in Scheme 1, 80 mg cobalt acetate was ultra-
which makes obtained Co3O4 material show stable elec- sonically dissolved in the solution (1 ml distilled water and
trochemical performances. In particular, after 300th cycle, 20 ml ethanol) and 1 ml ammonia (NH3·H2O) was put into
the reversible capacity of the as-obtained Co3O4 gradually the above solution drop by drop. Afterward, the above solu-
increases up to 471 mAh g−1 at 2 A g−1. Compared to the tion was needed to be stirred magnetically for 0.5 h to gain
other studies for Co3O4, the advantages of this work can be a uniform solution. The solution was placed in an autoclave
mainly expressed as follows: (1) The preparation method for reaction kettle and increased to 80 °C for 8 h. Subsequently,
Co3O4 is simple and facile, without involving any carbon the reaction temperature went up to 150 °C for 3 h. After
coating and pyrolysis process; (2) the uniform-sized Co3O4 being cooled down, the obtained dark solutions were cen-
nanoparticles accelerate Li-ion and electron transfer, which trifuged, washed with water and ethanol for three times, and
contributes to achieving high rate performance; and (3) the dried in vacuum at 60 °C overnight.
electrochemical performance of the as-obtained Co3O4 is
superior and can be improved with the increase in cycles 2.2 Electrochemical Testing
(383–471 mAh g−1 from the first cycle to the 300 cycles at
2 A g−1). The electrochemical measurements of the Co 3O 4 were
According to the previous literature on developing conducted in CR2032 coin-type batteries. For preparing
nanomaterials as anodes for LIBs, Co3O4 nanoparticles working electrodes, a mixture of 80 wt% active mate-
still show some obvious properties. For one thing, many rial, 10 wt% polyvinylidene fluoride (PVDF), and 10
nanomaterials as anodes usually need the hybridization of wt% acetylene black in N-methyl-2-pyrrolidone (NMP)
a variety of materials or addition of coated carbon followed was uniformly pasted onto a pure Cu foil and then dried
by calcination [22, 23]. For another, TiO2@SnO2 nanofibers at 80 °C in vacuum. Afterward, all coin batteries were
delivered a specific capacity of 378 mAh g−1 at a current fabricated in an Ar-filled glove box using the as-synthe-
density of 2 A g−1 [24], while in our study, a high capacity sized Co 3O 4 as the active electrodes (the mass loading
of 471 mAh g−1 could be obtained by Co3O4 nanoparticles was determined to be 1.0 mg cm−2), Li foil as a counter-
at 2 A g−1. Meanwhile, Zan et al. reported that SnO2/Fe2O3 electrode, and Celgard-2400 as the separator. The elec-
hybrid nanofibers demonstrated an outstanding cycling trolyte was 1 M LiPF 6 dissolved in ethylene carbonate
stability in contrast with pure SnO2 [23], so we can also (EC)/dimethyl carbonate (DMC)/ethyl methyl carbonate
add another transition metal oxide into Co3O4 to further (EMC) (1:1:1 by volume) with 2% VC. Electrochemical

Scheme 1 Illustration of synthesis process for Co3O4 nanoparticles

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Hydrothermal Preparation of Homogeneous Cobalt Oxide Nanomaterials as Stable Anodes for… 385

tests were performed on the NEWARE battery tester rang- 3 Results and Discussion
ing from 0.01 V to 3.0 V, and cyclic voltammetry investi-
gations are performed at a scan rate of 0.1 mV s−1. The X-ray powder diffraction (XRD) pattern of the as-
obtained Co3O4 is depicted in Fig. 1a. All the diffraction
peaks can be corresponding to the cubic phase of Co3O4
2.3 Materials Characterizations [25]. Meanwhile, no additional peaks can be seen in the
XRD pattern, revealing the high purity of the material. SEM
The XRD measurement was investigated at a scan rate was used to observe the morphology of a typical Co3O4
of 2° min−1 by a TD-3500 powder X-ray diffractometer sample. Figure 1b shows that large amount of Co3O4 nano-
(Tongda, China) with Cu-Kα radiation. The morphology particles agglomerate to some extent. The more detailed
and crystal structure of the materials were studied apply- information about the chemical composition and elemental
ing a Hitachi S-4800 scanning electronic microscope valence state of the Co3O4 nanoparticles was investigated
(SEM) and a FEI Tecnai G2 20 transmission electron by X-ray photoelectron spectroscopy (XPS). In Co 2p spec-
microscope (TEM) (Hillsboro, OR, USA). The X-ray pho- trum (Fig. 1c), there are two strong peaks with the binding
toelectron spectroscopy (XPS) was conducted on a Kratos energy at 795.4 eV and 780.3 eV, which are ascribed to the
XSAM 800 spectrometer (Manchester, UK). Co 2p1/2 and Co 2p3/2 spin–orbit peak of Co3O4, respectively
[26]. The binding energy difference between the peaks of Co
2p1/2and Co 2p3/2 is almost 15 eV, suggesting the presence of

Fig. 1 XRD pattern of Co3O4 a, SEM image of Co3O4 b, Co 2p c and O 1 s d spectra of Co3O4

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386 J. Ou et al.

Co2+ and Co3+ species in the sample [27].The peaks at about lattice planes (311) and (111) of Co3O4 crystal, respec-
803 eV and 787 eV are associated with the Co 2p1/2and Co tively [33]. The STEM element mapping analysis (Fig. 2c)
2p3/2 shake-up satellite of Co3O4, respectively [28]. Addi- further discloses the coexistence and evenly distribution
tionally, the peak located at about 707 eV is described as of cobalt and oxygen elements for Co3O4.
the Auger peak of cobalt [29]. The O 1s displayed in Fig. 1d The cyclic voltammetry (CV) profiles of Co 3 O 4
can be fitted into three major parts. The peaks at about electrode for the initial three cycles at a scan rate of
532.0 eV and 533.6 eV are associated with oxygen vacancy 0.1 mV s−1 ranging from 0.01 to 3.0 V are exhibited in
and absorbed oxygen, respectively, and the peaks centered Fig. 3a. In the first cycle, a strong cathodic peak appears
at 529.6 eV and 530.9 eV are both due to lattice oxygen at 0.8 V, which is ascribed to the reduction of cobalt ions
[30, 31]. Besides, the peak with a higher binding energy of to Co metal, the generation of amorphous Li2O, and the
531.6 eV may be attributed to the hydroxyl groups (OH) generation of solid–electrolyte interface (SEI) film [34,
[32]. 35]. Another inconspicuous cathodic peak was centered
Figure 2a depicts a low-magnification TEM image of at 1.7 V (disappeared in the subsequent cycles), which
Co3O4, from which it can be seen that Co3O4 nanoparticles may be because a small number of lithium ions enter the
are uniformly distributed without any obvious aggrega- crystal structure of Co 3O 4 [36]. Besides, there are two
tion. The high-resolution TEM (HRTEM) image of Co3O4 tiny peaks located at 1.4 and 2.0 V in first anodic scan,
displayed in Fig. 2b clearly further shows the homoge- which pertains to CoOx (0 < x < 1) and the oxidation pro-
neously Co3O4 nanoparticles with small particle sizes of cess of Co to Co3O4, respectively [37, 38]. The intensities
approximately 4–9 nm, which is consistent with Fig. S1. of the cathodic peaks are significantly weakened in the
Additionally, Co3O4 possesses two interplanar spacings other cycles because the SEI film is formed between the
of 0.23 and 0.46 nm, which is in accordance with specific

Fig. 2 TEM images a, b and STEM element mapping images c of the Co3O4. Inset in b showing the HRTEM image of Co3O4

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Hydrothermal Preparation of Homogeneous Cobalt Oxide Nanomaterials as Stable Anodes for… 387

Fig. 3 Electrochemical behaviors of Co3O4 anode materials, CV curves of Co3O4 materials during the initial three cycles a,charge and discharge
curves at a current density of 50 mA g−1 b, rate property at different current densities c and the cycling performances during 300 cycles at 2 A
g−1 d

electrolyte and nanostructured electrode [9]. Generally, of 556, 635, 656, and 690 mAh g−1, respectively, which
the electrochemical reactions involved can be illustrated indicates that Co3O4 is inclined to possess good capacity
as follows [39]: retention as well as much higher capacity. As demonstrated
in Fig. 3c, the rate property of Co3O4 is evaluated at differ-
Co3 O4 + 8Li+ + 8e− → 3Co + 4Li2 O ent rates ranging from 0.05 A g−1 to 5 A g−1. The average
reversible capacities are 753, 681, 614, 475, 462, 337, and
Figure 3b depicts the charge–discharge profiles of Co3O4 122 mAh g−1 at 0.05, 0.1, 0.2, 0.5, 1, 2, and 5 A g−1, respec-
with a current density of 50 mA g−1 ranging from 0.01 V tively. Impressively, the average reversible capacity of 695
to 3 V. It can be clearly observed that a well-defined long mAh g−1 with the 92.3% of the initial reversible capacity
potential plateau is at about 1.1 V, which is due to the reduc- can still be obtained when it is recovered to 0.05 A g−1,
tion of the intermediate LixCo3O4 to metallic Co [40, 41]. which is indicative of a fascinating recovering ability of the
The first charge and discharge capacities are 599 and 782 electrode. The cycling property of the Co3O4 is conducted
mAh g−1, respectively, accompanied by a Columbic effi- at 2 A g−1 in Fig. 3d. Generally, after 300th cycle, Co3O4
ciency (CE) of 76.6%. The first irreversible capacity loss electrode still works pretty stably with a reversible capacity
and relatively low CE may arise from the generation of the of 471 mAh g−1 even at a high current density of 2 A g−1.
SEI layer at the electrolyte interface, lithium storage, and The phenomenon of gradually increasing reversible capacity
electrolyte decomposition [42–44]. In the 2nd, 10th, 20th, upon cycling may be caused by the reversible generation of
and 50th cycles, Co3O4 electrode shows reversible capacities a polymeric gel-like film evolving from kinetic activation
during the charge/discharge process [45].

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The electrochemical impedance spectroscopy (EIS) Table 1 Kinetic parameters derived from the Nyquist plots of the
investigations were conducted at different cycles (10th, Co3O4 after different cycles
30th, and 50th at 50 mA g −1) in the frequency in the Cycles Rs (Ω−1) RSEI (Ω−1) Rct (Ω−1)
range of 100 kHz and 10 MHz for the sake of illuminating
10th 4.033 6.804 43.81
charge transfer and Li+ diffusion kinetics. As illustrated
30th 5.78 9.827 13.21
in Fig. 4, all the Nyquist plots present similar shape fea-
50th 5.848 7.589 11.14
ture of two depressed semicircles in the high-/medium-
frequency regions followed by a low-frequency linear tail.
The first semicircle in the high frequency is associated
with SEI resistance (R SEI), the second semicircle across 4 Conclusion
the medium-frequency region denotes charge transfer
impedance (Rct) in the interface between the electrode and In this work, a facile and simple hydrothermal strategy for
electrolyte, while the low-frequency linear tail is regarded the synthesis of Co3O4 nanoparticles is described. Such
as the Warburg impedance (Qw) revealing the solid-state Co3O4 nanoparticles with uniform size provide beneficial
Li+ diffusion process within bulk electrodes [8, 46, 47]. transport kinetics for both Li-ions and electrons. As a result,
In general, the intercept of the first semicircle at the real Co3O4 electrode provides growing cycling performances
axis (Z’) suggests the electrolyte resistance (Rs) [17, 48]. (about 471 mAh g−1 at 2 A g−1 after 300 cycles) and a
Based on remarkable capacity retention (92.3% of the initial capac-
the equivalent circuit, the fitted physical parameters ity when it returns to 50 mA g−1). In terms of the facile
are summarized in Table1. Furthermore, the SEI capaci- preparation and stable electrochemical properties as shown,
tance and interfacial capacitance can be defined as Q SEI this simple approach to prepare nanoparticles can be fur-
and Q d, respectively [49]. It is worth mentioning that ther applied in other transition metal oxides and serve as a
the Co3O4 takes possession of the lowest charge transfer promising strategy to explore alternative anode materials for
impedance (11.14 Ω) after 50 cycles, accounting for the applications in new-generation LIBs.
improved charge transfer activity at the interface between
the Co 3 O 4 nanoparticles and the electrolyte with the Acknowledgements This work was financially supported by the
increase in the cycle times. These results can be con- Science & Technology Department of Sichuan Province (No.
2019YJ0665).
firmed with the results of the cycling performances in
Fig. 3b and d. Notably, a maximum slope can be observed
at the 50th cycle, which may correspond to the lowest
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Fig. 4 EIS of Co3O4 electrode at 10th, 30th, and 50th cycles at 50 mA g−1 with the equivalent circuit

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Hydrothermal Preparation of Homogeneous Cobalt Oxide Nanomaterials as Stable Anodes for… 389

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