Materials Letters 166 (2016) 255–258

Contents lists available at ScienceDirect

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

One-pot synthesized ultrathin MnO2 nanorods as advanced electrodes

for high-performance supercapacitors
Min Lu a,b, Yang Lu a,b, Kangwen Qiu a,b, Jinbing Cheng a,b, Hailong Yan a,b, Yongsong Luo a,b,n
a
School of Physics and Electronic Engineering, Xinyang Normal University, Xinyang 464000, PR China
b
Key Laboratory of Advanced Micro/Nano Functional Materials, Xinyang Normal University, Xinyang 464000, PR China

art ic l e i nf o a b s t r a c t

Article history: Novel ultrathin MnO2 nanorods are successfully prepared by a one-pot hydrothermal process, which
Received 14 October 2015 endows with porous one-dimensional (1 D) nanostructures. As a result, the MnO2 nanorods show good
Received in revised form electrochemical performance as electrode materials for supercapacitors, including high specific capaci-
9 December 2015
tance of 820.8 F/g, long life over 5000 cycles, and good rate capability (562.5 F/g at 10 A/g). The fabri-
Accepted 23 December 2015
cation strategy present here is facile, cost-effective, and can offer a way for energy storage device ap-
Available online 23 December 2015
plications.
Keywords: & 2015 Elsevier B.V. All rights reserved.
MnO2
Ultrathin nanorods
Nanocrystalline materials
Hydrothermal method
Energy storage and conversion

1. Introduction
Supercapacitors (SCs) are powerful energy storage systems that
fill the gap between batteries and conventional capacitors in terms
of their specific energy and specific power [1,2]. However, the
current commercial SCs are mainly based on carbonaceous anode
materials which deliver low theoretical specific capacities, and
their capabilities are far from meeting the growing demand for
electric vehicle and large energy-storage devices [3,4]. With the
growing concerns over environmental pollution, metal chalcogen
elements have attracted increasing attention [5,6]. For instance,
MnO2 are considered as alternative electrode materials for su-
percapacitors due to their ultrahigh theoretical capacitance
(1370 F/g), low cost, natural abundance, environmental friendli-
ness and wide potential window [7]. Unfortunately, MnO2 is
hampered by its lower electronic and ionic conductivities and
large volume variations during charge–discharge process, result-
ing in the destruction of the structure [8–10].
In order to overcome these challenges, lots of studies have been
carried out. After extensive literature review, the relevant solving
strategies can be summarized as following: the first one is to
fabricate nanostructured MnO2 materials, such as nanowires, na-
noflakes, and nanotubes, have been comprehensively investigated
n were collected and washed by centrifugation for several cycles
Corresponding author at: School of Physics and Electronic Engineering, Xinyang
Normal University, Xinyang 464000, PR China.
E-mail address: ysluo@xynu.edu.cn (Y. Luo).
[11,12], which usually offer large surface area and free space for
accommodation of the volume change during cycling and short
path length for electrolyte diffusion; the second one is to grow
nanostructured MnO2 material directly on a conducting substrate,
which greatly improve the electric and physical contact between
the active material and the current collector. Although these ap-
proaches have effective improved the specific capacitance and
cycling performance of the MnO2 electrodes, they always involve
an excessive use of organic agents, complicated preparation pro-
cess, low productivity, etc.
In this work, ultrathin MnO2 nanorods were synthesized by a
facile, low-cost hydrothermal method without using any surfac-
tant. The electrochemical measurements indicate MnO2 nanorods
exhibit high specific capacitance and long stability.
2. Experimental section
2.5 mmol KMnO4 and 1 mL concentrated HCl were mixed with
45 mL deionized water and stirred for 30 min to form a precursor
solution, which was then transferred into a 50 mL Teflon-lined
stainless steel autoclave. The autoclave was sealed and hydro-
thermally treated at 140 °C for 12 h. After the autoclave was cooled
naturally to room temperature, samples depositing at the bottom
using deionized water and absolute ethanol. The as-synthesized
samples were then dried in 60 °C.

http://dx.doi.org/10.1016/j.matlet.2015.12.099
0167-577X/& 2015 Elsevier B.V. All rights reserved.
256 M. Lu et al. / Materials Letters 166 (2016) 255–258

Fig. 2. SEM images (a–d) and TEM images (e, f) of the MnO2 nanorods at different magnifications.

Fig. 1. (a) XRD patterns of α-MnO2; (b) Raman spectra of α-MnO2.

 M. Lu et al. / Materials Letters 166 (2016) 255–258 257

Fig. 3. Electrochemical characterization of MnO2 nanorods as supercapacitors material: (a) CV curves at different scan rates; (b) charge/discharge voltage curves at different
current densities; (c) the capacitance of the nanorods at different current densities; and (d) cycling performance of the nanorods with current density of 5 A/g (corre-
sponding charge/discharge curves of the first 8 and last 8 cycles of the MnO2 electrode in inset).

The phase structures of the products were characterized by
powder X-ray diffraction (XRD) on a Bruker D8 Advance X-ray
diffractometer. The morphologies were examined by field emis-
sion scanning electron microscopy (FESEM, Hitachi S-4800) and
transmission electron microscopy (TEM, JEOL JEM-2010). Raman
spectra were recorded on an INVIA Raman microprobe (Renishaw
Instruments, England). Nitrogen adsorption/desorption isotherms
were measured at 77 K with micrometrics ASAP 2020 analyzer.
The specific surface area was calculated from the adsorption curve
by the Barrett-Joyner-Halenda (BJH) method.
Electrochemical measurements were conducted on a CHI660E
electrochemical workstation by using a three-electrode cell. Car-
bon black was used as conductor, and polytetrafluoroethene was
used as adhesion agent. Active material (MnO2 nanorods,  3 mg),
carbon black and polytetrafluoroethene with a weight ratio of
80:10:10 were mixed. The polyvinylidene fluoride was added to
the solid mixture to form mash. Then the mash was pressed onto a
nickel foam (ca. 1 cm2) under 10 MPa for 10 min, and dried at 80 °C
overnight. The nickel foam with MnO2 film, a Pt foil and Ag/AgCl
electrode were used as the working electrode, the counter elec-
trode and the reference electrode respectively. 1 M KOH aqueous
solution was used as an electrolyte.
3. Result and discussion
Fig. 1a shows the XRD pattern of the synthesized nanorods
where the diffraction peaks corresponded to pure tetragonal
phases of α-MnO2 (JCPDS 44-0141). The structural features of the
MnO2 are further confirmed by Raman measurements. As shown
in Fig. 1b, the three Raman bands located at 501, 575, and
645 cm 1 are in good agreement with the three major vibrational
features of the birnessite-type MnO2 compounds [13].
Fig. 2a–d shows the SEM images of the resultant MnO2 sample
at different magnifications. According to the SEM observations, it
displays that the as-prepared MnO2 product is composed of
countless rod-like aggregates, which have flat and smooth surfaces
and their typical size is in the range of 1–2 mm in length and 25 nm
in diameter, nearly all of them hold the same morphology. The
MnO2 nanorods form an ultrathin surface layer, which is capable of
contributing to interfacial electrochemical reactions and provides
a large electrode surface area [14]. The structure and morphology
of the MnO2 nanorods were further investigated by TEM. Fig. 2e
and f show TEM images of the MnO2 nanorods in different mag-
nifications. From Fig. 2f, the obvious contrast between the center
and the edge indicates the ultrathin feature and porous structure.
Another factor inducing the rod growth is suggested by Hartanto
et al. that the gas pressure in the synthesis environment of the
main matrix can cause growth of nanorods [15]. When the mate-
rial is used as an electrode of SCs, such a porous structure could
effectively endure the volume change during discharging and
charging and promote the diffusion rate of the electrolyte. The
ultrathin nanorods are future investigated by BET measurements
(Fig. S1). The BET specific surface area is calculated to be ca.
89.2 m2 g 1. The mesoporous structure shows a narrow pore
diameter (7 nm) and a large BET specific surface area
(89.2 m2 g 1).
Cyclic voltammetry (CV) measurement is a suitable tool to
258 M. Lu et al. / Materials Letters 166 (2016) 255–258
characterize the capacitive behavior of electrode materials. Fig. 3a
shows the CV curves of the MnO2 electrode conducted in the po-
tential region of 0–0.8 V with scan rates ranging from 5, 10, 20, 30
and 50 mV/s, respectively. No peaks are presented, indicating that
the electrode is charged and discharged at a pseudo-constant rate
over the complete voltammetric cycle. The rectangular CV shape
remains very well even at a high scan rate of 50 mV/s, suggesting
the electrode possesses excellent rate capability desirable for high-
power supercapacitors. Fig. 3b shows the galvanostatic charge–
discharge (CD) curves of the MnO2 electrode at current densities of
1, 2, 3, 5 and 10 A/g, respectively. A linear variation of the potential
during both charging and discharging processes is observed for the
MnO2 nanorods electrode, and the CD curves are almost linear and
symmetrical, which is a typical characteristic of an ideal capacitor
behavior. The specific capacitances calculated from the discharge
curves are 820.8, 757.5, 718.1, 587.5, 562.5 F/g at the current
densities of 1, 2, 3, 5, 10 A/g, respectively. The results present a
trend that the specific capacitance gradually decreases with in-
crease of the current density. The decrease in capacitance suggests
that parts of the surface of the electrode are inaccessible at high
charge/discharge rates [16,17]. Remarkably, Over this current
density range, the specific capacitance remains 68% of its initial
value (Fig. 3c), implying the good ion diffusion and electron
transport at a high current density.
The cycle stability of the electrode is another important para-
meter for supercapacitor. The performance of the electrode was
measured with a current density of 5 A/g for 5000 cycles. After-
ward, the capacitance was kept at 98.5% of the initial capacitance,
indicating excellent long-term stability from the fabricated ultra-
thin nanorods electrode. Importantly, the charge–discharge curves
are still keeping quite symmetric after 5,000 cycles test (inset in
Fig. 3d is the charge/discharge curves of the first 8 cycles and last
8 cycles for the MnO2 electrode).
The cycling performance of the MnO2 electrode at progressively
increased current density was recorded in Fig. S2. During the first
300 cycles with a charge/discharge density of 1 A/g, the MnO2
show a capacitance of 820.8 F/g. In the following 1,500 cycles, the
charge/discharge rate changes successively. This porous 1D na-
nostructured electrode always demonstrates stable capacitance.
After 1,800 cycles, with the current rate being again decreased
back to 1 A/g for another 300 cycles, a capacitance of 818.5 F/g can
be recovered without noticeable decrease, which demonstrates
that the nanostructure has excellent rate performance and
cyclability.
4. Conclusions
Porous ultrathin MnO2 nanorods were successfully prepared by
a facile hydrothermal method. TEM and BET analysis on the pro-
ducts demonstrated their ultrathin and porous characteristics. The
products exhibit excellent electrochemical performance as super-
capacitor with high specific capacitance and long stability, which
result from its special 1 D porous structure.
Acknowledgments
This work is financially supported by the National Natural
Science Foundation of China (Nos. U1304108, U1204501 and
21373107).
Appendix A. Supplementary material
Supplementary data associated with this article can be found in
the online version at http://dx.doi.org/10.1016/j.matlet.2015.12.
099.
References
[1] L.Y. Gong, X.H. Liu, L.H. Lu, Mater. Lett. 67 (2012) 226–228.
[2] S.X. Liu, L.F. Hu, X.J. Xu, A.A. Al-Ghamdi, X.S. Fang, Small 11 (2015) 4267–4283.
[3] D. Villers, D. Jobin, C. Soucy, D. Cossement, R. Chahine, L. Breau, D. Bélanger, J.
Electrochem. Soc. 150 (2003) A747–A752.
[4] F. Fusalba, H.A. Ho, L. Breau, D. Be, Chem. Mater. 12 (2000) 2581–2589.
[5] X.J. Xu, L.F. Hu, N. Gao, S.X. Liu, S. Wageh, A.A. Al-Ghamdi, A. Alshahrie, X.
S. Fang, Adv. Funct. Mater. 25 (2015) 445–454.
[6] W. Wei, X. Cui, W. Chen, D.G. Ivey, Chem. Soc. Rev. 40 (2011) 1697–1721.
[7] S.W. Zhang, G.Z. Chen, Adv. Energy Mater. 3 (2008) 186–200.
[8] C.Y. Guo, H. Li, X. Zhang, H.H. Huo, C.L. Xu, Sens. Actuators B: Chem. 206 (2015)
407–414.
[9] T. Zhai, S.L. Xie, M.H. Yu, P.P. Fang, C.L. Liang, X.H. Lu, Y.X. Tong, Nano Energy 8
(2014) 255–263.
[10] Y.Y. Li, Q.W. Zhang, J.L. Zhu, X.L. Wei, P.K. Shen, J. Mater. Chem. A 2 (2014)
3163–3168.
[11] W.X. Tang, X. Shan, S.D. Li, H.D. Liu, X.F. Wu, Y.F. Chen, Mater. Lett. 132 (2014)
317–321.
[12] H.L. Li, L.X. Jiang, Q.L. Cheng, Y. He, V. Pavlinek, P. Saha, C.Z. Li, Electrochim.
Acta 164 (2015) 252–259.
[13] D.Z. Kong, J.S. Luo, Y.L. Wang, W.N. Ren, T. Yu, Y.S. Luo, Y.P. Yang, C.W. Cheng,
Adv. Funct. Mater. 24 (2014) 3815–3826.
[14] Y.S. Luo, J. Jiang, W.W. Zhou, H.P. Yang, J.S. Luo, X.Y. Qi, H. Zhang, Y.W.Y. Denis,
C.M. Li, T. Yu, J. Mater. Chem. 22 (2012) 8634–8640.
[15] S. Demirel, E. Oz, E. Altin, S. Altin, A. Bayri, P. Kaya, S. Turan, S. Avci, Mater.
Charact. 105 (2015) 104–112.
[16] K.W. Qiu, Y. Lu, D.Y. Zhang, J.B. Cheng, H.L. Yan, J.Y. Xu, X.M. Liu, J.K. Kim, Y.
S. Luo, Nano Energy 11 (2015) 687–696.
[17] C.J. Hung, P. Lin, T.Y. Tseng, J. Power Sources 259 (2014) 145–153.