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Synthesis of Mn3O4 nanowires and their transformation to LiMn2O4

polyhedrons, application of LiMn2O4 as a cathode in a lithium-ion battery†
Xing Zhang,a Zheng Xing,a Yang Yu,a Qianwen Li,a Kaibin Tang,a Tao Huang,a Yongchun Zhu,*a Yitai Qian*ab
and Dong Chenc
Received 29th September 2011, Accepted 9th November 2011
DOI: 10.1039/c1ce06289a

Mn3O4 nanowires with diameter of
15 nm and a length of up to several micrometres have been
hydrothermally synthesized at 200  C for 15 h without any surfactants. It was investigated that during
the formation process of Mn3O4 nanowires the length of the nanowires increased while the diameter did
not obviously change. The coercivity of the Mn3O4 nanowires is up to 5600 Oe at 5 K. As these Mn3O4
nanowires were treated with LiOH by solid state reaction at 750  C for 6 h, interconnected LiMn2O4
polyhedrons were obtained. The achieved discharge capacity of the LiMn2O4 polyhedrons was 115
mAh g1 and they retained 98.3% of this capacity after 60 cycles at 0.1 C.

Introduction diameters of 15–40 nm were prepared using Mn(Ac)3 in an

acetonitrile–water system.33 Until now, some Mn3O4 nano-
Hausmannite Mn3O4 is an intriguing composite and has a range of crystals of octahedrons3 and nanocubes4 were obtained via
versatile applications in many important fields, such as catalysts,1–4 hydrothermal routes. It is noted that these morphologies are all
microwave absorption,5 sensors,6 supercapacitors7–11 and anode induced by the inherent crystal habit of the tetragonal phase
materials.12,13 In particular, the Mn3O4 nanostructure is one of the Mn3O4. There is no report on crystal growth of Mn3O4 nano-
most promising raw materials, which can substitute for commer- wires in water without any template or surfactant.
cial manganese carbonate to produce LiMn2O4 with a smaller size. As for the synthesis of Li-Mn-oxide from Mn3O4 nanocrystals,
Li-Mn-oxides, are the most attractive lithium battery materials layer type LiMnO2 nanoparticles were prepared by treating
owing to their outstanding advantages in terms of low cost, high Mn3O4 powder at 170  C for 4 days in an autoclave.14 LiMn2O4
abundance, excellent cycle life and low toxicity.14–16 nanocrystals of spheres and octahedrons have been synthesized
Mn3O4 nanomaterials with various morphologies were using Mn3O4 colloidal spheres as the raw material by solid state
prepared, such as nanoparticles,8,17–22 nanorods,15,23–26 nano- reaction at 600 and 750  C, respectively.15
plates,6,27,28 octahedrons,6,9,13,29 nanocubes4 and hollow struc- Herein we present a simple hydrothermal route for the synthesis
tures.11,30 Also Mn3O4 nanowires have been synthesized by of Mn3O4 nanowires on a large scale. These nanowires possessed
various routes. For example, Mn3O4 nanowires with diameters an average diameter of
15 nm and length of up to several
of 40–80 nm have been prepared by solid state reactions using micrometres. Magnetism measurements show that the coercivity
MnCO3 as a precursor at 850  C for 2 h in NaCl flux in a tube is up to 5600 Oe at 5 K. As these Mn3O4 nanowires were treated
electric furnace.31,32 Mn3O4 nanowires were also prepared in with LiOH by solid state reaction at 750  C for 6 h, closely packing
organic solvent systems and solvent-hydro systems. Mn3O4 LiMn2O4 polyhedrons were obtained. The capacity of LiMn2O4
nanowires with diameters of
100 nm have also been fabricated polyhedrons achieved 115 mAh g1 and retained 98% of this
by manganese(II) acetate in an oleic acid–oleylamine–xylene capacity after 60 charge–discharge cycles at 0.1 C.
system in an air atmosphere.28 Mn3O4 nanowires with diameters
of
12 nm were solvothermally synthesized using Mn(NO3)2 in
a dodecanol–oleylamine system.15 Mn3O4 nanowires with Experimental
All chemicals were of analytical grade and purchased from
a
Shanghai Chemical Industrial Corp. and used as received
Hefei National Laboratory for Physical Sciences at Microscale and
Department of Chemistry, University of Science and Technology of without further purification. A typical synthesis process was as
China, Hefei, Anhui, 230026, P. R. China. E-mail: ytqian@ustc.edu.cn; follows:
Fax: +86-551-360-7402; Tel: +86-551-360-1589
b
School of Chemistry and Chemical Engineering, Shandong University,
Jinan, 250100, P. R.China Synthesis of Mn3O4 nanowires
c
Jiangsu Highstar Battery Manufacturing CO., LTD,
† Electronic supplementary information (ESI) available: XRD patterns, In a typical experiment, MnSO4 (4 mmol), Na2B4O7 (1 mmol)
SEM, TEM images and discharge curves. See DOI: 10.1039/c1ce06289a and NaOH (4 mmol) were dissolved in 15 mL deionized water,

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respectively. To begin with, a 15 mL MnSO4 (0.27 M) solution phase. The lattice constants calculated from this pattern are a ¼
was quickly added into the Na2B4O7 (0.07 M) solution under  c ¼ 9.432 A,
5.745 A,  which could be indexed to the standard
magnetic stirring for at least 2 min, and the color of the mixture value of JCPDS No. 24-0734, (a ¼ 5.762 A,  c ¼ 9.469 A).

became white. Then a 15 mL NaOH (0.27 M) solution was added Fig. 1b and 1d exhibit the low resolution SEM and TEM
under magnetic stirring for at least 30 min and a brown mixture images of the product, respectively. It can be easily found that
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was formed. The obtained mixture was transferred into a 60 mL these nanowires, with a length of up to several micrometres,
autoclave with a Teflon liner. The autoclave was sealed and account for the majority of the product obtained. Closer
maintained at 200  C for 15 h. After the autoclave was air-cooled inspection from high magnification images (Fig. 1c and 1e) reveal
to room temperature, the resulting product was filtered and that these nanowires possess a diameter of
15 nm. The structure
washed with deionized water and ethanol several times, then characterization of Mn3O4 nanowires was investigated in detail
dried under vacuum at 60  C for 12 h. by HRTEM microscopy. Fig. 1f is an HRTEM image of an
individual nanowire with a diameter of
7 nm. HRTEM reveals
Synthesis of LiMn2O4 polyhedrons that the interlayer spacing of nanowire is
0.30 nm, consistent
with the (112) plane lattice parameter of tetragonal phase
Typically, LiOH$H2O and the as-prepared Mn3O4 nanowires, Mn3O4. Based on the analyses of the HRTEM, the (112) layers is
mixed with a molar ratio, were added into 3 mL of high-purity almost perpendicular to the nanowire axis indicated by an arrow
ethanol under agitation and dried at room temperature. Then the in Fig. 1f.
mixed powder was calcined at 750  C in air for six hours (heating
rate 4  C min1).
Studies on the Mn3O4 nanowires growth process

Characterization To investigate the growth process of these nanowires, we have

studied the samples (taken at various stages of reaction) using
The X-ray powder diffraction (XRD) patterns were obtained on XRD and TEM. The XRD patterns in Fig. S1 show that longer
a Philips X’ Pert PRO SUPER diffractometer equipped with reaction times led to good crystallization. The products are
graphite monochromatized CuKa radiation (l ¼ 1.541874 A). amorphous (Fig. S1a†), when the reaction time is 0.5 h at 200  C.
The scanning electron microscopy (SEM) images were taken with As the time was prolonged, the intensity of (103), (211) and (224)
an X-650 scanning electron microanalyzer and a JEOL-JSM- peaks were obviously increased (Fig. S1b†).
6700F field emission scanning electron microscope. The trans- The Fig. 2 shows TEM images of the samples that were
mission electron microscopy (TEM) images were recorded on obtained after the hydrothermal reaction proceeded for 0.5, 1.0,
a Hitachi Model H-7650 transmission electron microscope, using
an accelerating voltage of 100 kV. The high-resolution trans-
mission electron microscopy (HRTEM) images and selected area
electron diffraction (SAED) patterns were taken on a JEOL 2010
high-resolution transmission electron microscope performed at
an acceleration voltage of 200 kV. The magnetic measurements
on a powdered sample were conducted using a commercial
superconducting quantum interference device (a SQUID
magnetometer, Quantum Design MPMS-XL).

Electrochemical investigation
Electrochemical measurements were performed using coin-type
2016 cells. The working electrode was constructed by making
a slurry of the active material, acetylene black, and poly-
vinylidene fluoride (PVDF) binder, using a weight ratio of
75 : 15 : 10. Lithium metal was used as the counter electrodes,
and the separator was a Celgard 2400microporousmembrane. A
1 mol L1 solution of LiPF6 dissolved in the mixture of ethylene
carbonate–dimethyl carbonate (EC–DMC), with a 1 : 1 volume
ratio, was used as the electrolyte. Cell assembly was carried out in
a glove box filled with high-purity argon gas. The charge–
discharge tests were performed within a range of 3.3–4.35 V at
different current densities.

Fig. 1 (a) XRD pattern of the prepared Mn3O4 nanowires, the inset in
Results and discussion (a) is the Mn3O4 spinel structure. (b) Low and (c) high magnification
Phase and morphology of the Mn3O4 SEM images of as-prepared Mn3O4 nanowires at 200  C for 15 h. (d) Low
and (e) high magnification TEM images, the inset in (e) is the SAED of
Fig. 1a shows the XRD pattern of the products obtained at 200 Mn3O4 nanowires. (f) HRTEM image analysis of single Mn3O4

C for 15 h. All the peaks can be indexed to the tetragonal Mn3O4 nanowire.

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6.0 and 12 h. After being heated for 0.5 h, a large amount of the pH value of the mixture was adjusted to 9.69 by using 0.267
brown solid product was generated, indicating the formation of M NaOH solution. Nanoparticles with a micrometre size were
Mn3O4 nanocrystals. Fig. 2a shows the initial product mainly obtained (see Fig. S3a†). Without adding Na2B4O7, at the same
consisted of nanofibers with a diameter of 15 nm and a length of time the pH value of mixture was 9.45, only nanoparticles and
100 nm. After 1.0 h, the length of the nanowire is 150 nm nanorods were obtained (see Fig. S3b†). It hints that the
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(Fig. 2b) and the diameter is still kept of 15 nm. Mn3O4 nano- Na2B4O7 plays an essential role in the synthesis process of the
wires with lengths of several micrometres were obtained when the nanowires. Its roles are similar to these of NaCl on the formation
reaction time was prolonged to 6 h, while the diameter did not of Ag nanowires.36,37 The experiment parameters between pH
obviously change. The nanowires grew much longer with the value and the morphology of the samples are shown in Table 1
diameter kept constant when the reaction time was 12 h (Fig. 2d). (see ESI†).
From the TEM images of the samples (Fig. 2) for the different In addition, as the formation of Mn3O4 nanowires involved
reaction times, we can observe that the diameter of the Mn3O4 the oxidation of Mn(II) ions by air, insufficient and excess
nanowires has no obvious change and the length of the nano- oxidation have some effect on the final product. When the
wires grew longer from 100 nm to several micrometres. This experiment was under N2, the morphology of the product was
growth mode was very similar to Fe3O4 and FeOOH 1-D nanowires and particles (see Fig. S4a†). When the final mixture
nanostructures.34,35 was stirred for 12 h in an air atmosphere, the morphology of the
In the reaction process to Mn3O4, initially, as the 15 mL product was nanoparticles (see Fig. S4b†). So the formation
Na2B4O7 (0.07 M) solution was added into the MnSO4 solution, process of Mn3O4 nanowires can be described as follows (Fig. 3).
the colour of the mixture became white. Then when a 15 mL
NaOH (0.267 M) solution was added, the brown mixture Magnetic property of Mn3O4 nanowires
appeared. The brown mixture was measured by XRD (see Fig. S2a
†), which indicated that the mixture is amorphous. According to The M versus H curves for the sample are selectively presented in
reference reports, Mn2+ and OH ions combined by added NaOH Fig. 4. The values of the coercivity are 780 Oe, 3600 Oe and 5600
solution to form white Mn(OH)2. The Mn(OH)2 is not stable in air Oe, measured at 35, 10, and 5 K, respectively. The data exhibit
atmosphere and is oxidized to a brown mixture which is amor- a higher coercivity in comparison with the values reported for
phous Mn3O4.3,28 Similarly, the brown mixture in our reaction is bulk Mn3O4 (2800 Oe at 4.2 K) and are similar to the reported
considered to be amorphous Mn3O4. The TEM image shows that Mn3O4 nanowires with a diameter of 70 nm (5670 Oe at 5 K).38,39
the morphology of the brown product is a nanowire with a diam- For the large coercivity of Mn3O4 nanowires, one feasible
eter of several nanometres and a length of 100 nm (see Fig. S2b†). explanation is that the coercive field originates from the
Based on the above results, together with Fig. 2, the growth magnetization inversion related to the high shape anisotropy and
process of Mn3O4 nanowires indicates that their growth involves small size to form single magnetic domains.40,41
two stages: 1) the formation of amorphous nanowires, which is
a crucial step in the formation of the crystallization nanowires; 2) Phase and morphology of LiMn2O4 polyhedrons
the crystallization of the amorphous nanowires to single crystal
LiMn2O4 polyhedrons were obtained by a simple solid-state
nanowires with the increase of the length. It could be believed
reaction using as-obtained Mn3O4 nanowires and a lithium
that the formation of Mn3O4 nanowires followed the Ostwald
source such as LiOH$H2O at 750  C for 6 h. The XRD pattern
ripening process.34,35
(Fig. 5a) of the products after treatment is in good agreement
It should be pointed out that Na2B4O7 plays an important role
with the standard pattern for LiMn2O4 (JCPDS No. 35-0782),
in the synthesis of Mn3O4 nanowires. In the absence of Na2B4O7,
with no peaks of the Mn3O4 phase detected. Fig. 5b is a SEM
image for the LiMn2O4, which shows that the products consist of
polyhedrons with a size of 200 nm–1000 nm. Interestingly, these
LiMn2O4 polyhedrons are closely packed.

Electrochemical properties of LiMn2O4 polyhedrons

Fig. 5c is the discharge curves for the LiMn2O4 polyhedrons at
different constant rates of 0.1 C, 0.2 C and 0.5 C. The discharge

Fig. 2 TEM images of the products obtained by the hydrothermal

reaction at 200  C for different reaction times: (a) 0.5, (b) 1.0, (c) 6 and (d) Fig. 3 Schematic illustration the formation process in the synthesis of
12 h. Mn3O4 nanowires.

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Conclusions
In conclusion, Mn3O4 nanowires, with a diameter of
15 nm and
a length of up to several micrometres, were prepared on a large
scale through a hydrothermal process without any surfactants.
Magnetism measurements show that the coercivity of the Mn3O4
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nanowires is up to 5600 Oe at 5 K. For further electrochemical

application, Mn3O4 was used as the raw material to fabricate
LiMn2O4 polyhedrons by a solid state reaction. The as-obtained
LiMn2O4 polyhedrons showed that an initial capacity of 115
mAh g1 and a retained capacity of 113 mAh g1 after 60 cycles
(98.3% capacity retention) at a rate of 0.1 C.

Fig. 4 Hysteresis loops for Mn3O4 nanowires obtained at 5 K (-), 10 K Acknowledgements

(C) and 35 K (:).
The authors would like to acknowledge support from the National
Natural Science Fund of China (No. 91022033), the 973 Project of
China (No. 2011CB935901) and the Fundamental Research
Funds for the Central Universities (No. WK 2340000027).

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