Int. J. Electrochem. Sci.

, 8 (2013) 2313 - 2329

International Journal of
ELECTROCHEMICAL
SCIENCE
www.electrochemsci.org

Hierarchical Al-doped and Hydrogenated ZnO

Nanowire@MnO2 Ultra-Thin Nanosheet Core/Shell Arrays for
High-Performance Supercapacitor Electrode
Mingpeng Yu1,2, Hongtao Sun2, Xiang Sun2, Fengyuan Lu2, Gongkai Wang2, Tao Hu2,
Hong Qiu1 and Jie Lian2,*
1
Department of Physics, School of Mathematics and Physics, University of Science and Technology
Beijing, 30 Xueyuan Road, Haidian District, Beijing 100083, China
2
Department of Mechanical, Aerospace & Nuclear Engineering, Rensselaer Polytechnic Institute,
Troy, New York, 12180, USA
*
E-mail: LIANJ@rpi.edu

Received: 16 October 2012 / Accepted: 7 December 2012 / Published: 1 February 2013

ZnO@MnO2 and Al-doped ZnO (AZO)@MnO2 hybrid electrodes in core/shell geometries have been
synthesized on stainless steel substrates by a scalable low-cost solution route. Cyclic voltammogram
(CV) and galvanostatic (GV) charge-discharge measurements demonstrated that the AZO@MnO2
hybrid electrode exhibited superior capacitive properties, in 1M Na2SO4 aqueous solution, to the
ZnO@MnO2 electrode. The specific capacitance based on total electrode mass is estimated to be 275
F/g at a current density of 2 A/g. The AZO@MnO2 electrode also displays an excellent long-term
cyclic stability at a current density of 10 A/g with less than 3% loss after 2000 charge-discharge cycles.
A ~35% capacity retention was observed at 60A/g, which is over 400% specific capacitance increment
compared with the ZnO@MnO2 electrode. The superior electrochemical capacitive properties of the
AZO@MnO2 over ZnO@MnO2 can be attributed to the enhanced electrical conductivity in the core
nanowire, as a result of Al doping and hydrogenation. The low cost fabrication combined with the
excellent capacitive properties indicates that the AZO@MnO2 hybrid architecture can serve as a
promising electrode material for supercapacitors as well as other electrochemical energy
storage/conversion devices.

Keywords: ZnO nanowires, MnO2, core/shell hybrid architecture, supercapacitors, energy storage

1. INTRODUCTION

The development of high performance electrode materials is critical for advanced energy
storage systems including supercapacitors and batteries in delivering simultaneously high energy
Int. J. Electrochem. Sci., Vol. 8, 2013 2314

density and power density. It was reported that 90% of the capacitor cost resides in the electrode
material [1], and it is a challenge to find high performance electrode materials (i.e., high specific
capacitance as well as good rate capability) accompanied with low-cost, environmental benignity and
natural abundance. Three main categories of electrode materials are typically employed including
carbonaceous materials [2,3], conducting polymers [4,5], and metal oxides/hydroxides [6,7]. Among
various metal oxide/hydroxides electrodes, hydrous RuO2 is the state-of-the-art pseudocapacitor
material with a specific capacitance as high as 1300 F/g [7]. However, the high cost and environmental
toxicity of Ru as well as use of strong acidic electrolytes limit its practical applications. MnO 2, a
nontoxic 3d transition metal oxide with a high theoretical capacitance up to 1370 F/g, has attracted
much attention due to its low cost, good electrochemical reactivity, environmentally-friendly property
and enhanced safety during operations. Although MnO2 has been considered to be one of the most
attractive alternative to RuO2; however, the low electrical conductivity (in the range of 10-5-10-6 S/cm)
and poor rate performance of MnO2 electrodes have been their major challenges, limiting the rate
capabilities for high power and cycling performances. The achievable capacitance is highly dependent
on morphology, specific surface area and electrical conductivity [8].
For various energy storage architectures, nanostructured electrode materials are very useful in
facilitating mass transport, ion diffusion and electron transfer and thereby improving electrochemical
performances [9-13]. In order to improve the electrical conductivity of MnO2-based electrodes, various
MnO2-conductive matrix (carbonaceous materials [14-19] and conducting polymers [20-22]) hybrid
nanostructures have been proposed as suitable approaches to boost the electrochemical performance.
These methods could enhance the electrical conductivity and increase the active sites as well as the
homogeneity of the electrochemical reaction, thus improving electrochemical performance of the
electrode materials. Particularly, novel nanostructured electrodes based on 1D nanowire/nanorod
arrays have attracted considerable attentions due to the synergic effect of the core/shell structures. By
constructing hierarchical core/shell structures with porous electroactive materials to improve high
transport rates of electrolyte ions and electrons, high specific capacitance have been obtained. For
example, hybrid nanostructures of Co3O4@MnO2 [23], CoO@NiHON [24], Zn2SnO4@MnO2 [25],
SnO2@MnO2 [26], CNT@RuO2 [27] have been investigated for supercapacitor applications and
improved performances have been demonstrated.
ZnO is a versatile material that can be easily fabricated with extremely low cost, and recently,
much effort has been put into the development of one-dimensional (1D) ZnO nanowire/nanorod array-
supported electrodes for electrochemical supercapacitors [28-30], utilizing its good electrical
conductivity. However, due to its intrinsic semiconductor in nature, it is possible to further increase
electrical conductivity of the ZnO nanowire/nanorod array-supported core/shell electrodes for more
effective ion diffusion and electron transfer and enhance energy and power densities [31]. 1D ZnO
nanowire with an appropriate amount of Al doping could provide an effective and facile way to
increase the electrical conductivity by more than two orders of magnitudes [32]. Furthermore, post-
growth hydrogen treatment is another simple and efficient method for the conductivity enhancement,
which were intensively investigated both theoretically and experimentally [33-36]. The conductivity of
ZnO could be enhanced by up to three orders of magnitude without significant changes in the structure
and crystal orientation of the wurtzite type ZnO nanostructures [36]. Additionally, annealing in a
Int. J. Electrochem. Sci., Vol. 8, 2013 2315

reducing atmosphere could also improve the conductive stability [37]. The approach of hydrogenation
was also applied in other transition metal oxides such as SnO2 and TiO2 electrodes exhibiting more
favorable electrochemical reactivity [38-40]. Very recently, Lu et al. [41] reported that hydrogenated
TiO2 nanotube arrays served as a good scaffold to support MnO2 nanoparticles, leading to a specific
capacitance of 912 F/g at a scan rate of 10 mV/s (based on the mass of MnO2 only).
Here, we report, for the first time, a approach in synergizing the Al-doping and hydrogenation
of the ZnO nanowires (hereafter referred to as AZO) to support redox active MnO2 nanoshell
electrodes in a core/shell geometry. This unique core/shell hybrid architecture displays several distinct
advantages as electrode materials such as: (1) single-crystalline quality AZO nanowires (see
Supplementary Information) serving as continuous electron transport pathways enabling faster electron
transferring; (2) AZO nanowires directly grown on the stainless steel current collector, thus avoiding
the use of polymer binder and conductive additives; (3) nanoporous ultrathin MnO2 nanosheets
facilitating ion diffusion and enabling a fast and reversible faradic reaction; and (4) core/shell
geometries offer large electrochemically active area and enhanced electron collection efficiency,
effectively combining high energy with high power characteristics (e.g., high specific capacity, good
rate capability and long cycle life).
By combining unique properties of individual constituents, much improved electrochemical
performance has been demonstrated for the AZO@MnO2 as compared with the control electrode
without Al-doping and hydrogenation. The specific capacitance can reach 275 F/g at a current density
of 2 A/g (based on total electrode mass) and at 60 A/g, ~35% capacity retention can be achieved. The
hybrid AZO/MnO2 core/shell electrode also displays remarkable rate capability and an excellent long
term cycle stability, promising for high performance supercapacitor applications. In addition,
theoretical calculations suggest that transition metal oxides possessing prominent theoretical
capacitance but more or less of low conductivity, such as TiO2, SnO2, Fe2O3, WO3, CuO, Ag2O, Cr2O3,
even IrO2 and RuO2, could become more conductive upon the hydrogenation of the host lattice [42].
Therefore, the hydrogenation approach reported here can be applicable to a wide range of energy-
storage electrode materials in improving the conductivity and enhancing their higher specific
capacitance and specific power.

2. EXPERIMENTAL SECTION

2.1 Synthesis of ZnO@MnO2 and AZO@MnO2 nanowire arrays

All chemical reagents were purchased from Sigma-Aldrich and used without further
purification. A two-step solution-based method was used for the fabrication of the core/shell hybrid
architecture, as illustrated in Scheme 1. Firstly, AZO and ZnO nanowire arrays grown directly on
stainless steel substrates were fabricated by a facile hydrothermal method (see Supplementary
Information). The AZO and ZnO nanowire arrays were then subjected to overnight immersion in a
0.04 M aqueous glucose solution, followed by a 3-hour post-annealing at 450°C in 4% H2 (balanced
with Ar) and pure Ar gases, respectively. For the AZO nanowire array, carbonization and
Int. J. Electrochem. Sci., Vol. 8, 2013 2316

hydrogenation processeswere achieved in one single treatment step. Secondly, the AZO@C and
ZnO@C nanowire arrays were immersed into a 0.03 M KMnO4 solution and sealed in a Teflon-lined
stainless steel autoclave at 160 °C for 5 hours.

Scheme 1. Schematic illustration of the fabrication processes of the hybrid electrode: (1) Carbon
coating; and (2) chemical reaction between carbon and KMnO4.

The reaction between carbon and KMnO4 could lead to in situ formation of porous ultrathin
MnO2 nanosheets on AZO and ZnO nanowire arrays [23,43,44] based on the following reaction:

4MnO4-+3C+H2O = 4MnO2+ CO32-+2HCO3- (1)

2.2 Structural characterization

The morphologies and microstructure of the as-prepared products were characterized by field
emission scanning electron microscopy (FESEM, Zeiss 1540 EsB), X-ray diffraction (XRD;
PANanalytical) at room temperature with Cu Kα radiation (wavelength = 1.54 Å), Raman
spectroscopy (Renishaw, 514 nm) and transmission electron microscopy (TEM, JEOL 2010) operated
at 200 keV. The chemical state of the products was characterized by X-ray photoelectron spectroscopy
(XPS, PHI 5000 Versa Probe).

2.3 Electrochemical measurements

The electrochemical measurements of cyclic voltammograms (CV) and galvanostatic

charge/discharge were conducted on an electrochemical workstation (Ametek, Princeton Applied
Research, Versa STAT 4) using a three-electrode configuration in a 1M Na2SO4 solution.
AZO@MnO2 and ZnO@MnO2 hybrid arrays on stainless steel substrates were used as working
electrodes directly. The reference electrode and counter electrode were SCE (saturated calomel
electrode) and platinum wire, respectively. CV tests were carried out over a voltage range of 0 to 0.8V
vs. SCE at various scan rates from 10 to 400 mV/s. Galvanostatic charge/discharge measurements
were conducted between 0 and 0.8 V vs. SCE at different current densities of 2-60 A/g.
Int. J. Electrochem. Sci., Vol. 8, 2013 2317

3. RESULTS AND DISCUSSION

Figure 1.(a) Optical images of stainless steel (SS) substrate (left), AZO nanowire array on SS (middle)
and AZO@MnO2 hybrid electrode on SS (right); (b-c) SEM images of the ZnO and AZO
nanowire arrays on SS, respectively; and (d) XRD patterns of the ZnO and AZO nanowire
arrays.

Fig. 1(a) shows optical images of a bare 0.5 inch diameter stainless steel substrate (left), ZnO
nanowire array on SS (middle) and AZO@MnO2 on SS (right). The color changed from white to dark
yellow reveals highly uniform thin films obtained. Fig. 1(b) and (c) show the FESEM images of the
ZnO and AZO nanowire arrays obtained by the hydrothermal method. The diameter and the length of
the ZnO nanowires were around 100 nm and 2 micrometer, respectively. Both ZnO and AZO nanowire
arrays are well aligned on the substrate. The tops of the pure ZnO nanowire arrays were well-defined
hexagons, indicating perfect hexagonal wurtzite structure; whereas AZO nanowire arrays are hexagon-
like with irregular edge profiles, probably due to the effect of Al doping. Fig. 1(d) shows the XRD
patterns of the ZnO and AZO nanowire arrays. No metallic Zn or Al characteristic peaks are observed.
Both products exhibit the same growth direction along [001] orientation, indicating Al-doping in ZnO
nanowires does not affect crystal orientation, the physical dimensions and microstructure of the ZnO
nanowires.
In order to investigate chemical state of Al and the chemical composition of AZO nanowires,
XPS measurement was conducted. The XPS survey spectrum from 100 to 1500 eV reveals the
Int. J. Electrochem. Sci., Vol. 8, 2013 2318

presence of Zn, O, Al and C, as shown in Fig. 2(a). The C signal may originate from adventitious
carbon contamination. The binding energy of Al-O for Al2p peak (74.6 eV) was clearly observed, as
shown in Fig. 2(b).

Figure 2. XPS results of the AZO nanowire arrays: (a) survey scan spectra; (b) Al 2p spectra; (c) Zn
2p spectra; (d) O 1s spectra; and (e) XPS spectra of Mn 2p of the AZO/MnO2.

Moreover, the Al 2p peak exhibits a symmetry feature with a FWHM of 1.57 eV, and no
metallic aluminum peak centered at 72.7 eV appears in the spectrum [45]. The one valence state of
Al3+ indicates that Al elements have been successfully doped into the ZnO nanowire lattice. Zn 2p and
O 1s spectra are drawn in Fig. 2(c) and (d), respectively. It can be seen that the XPS peak positions of
Zn 2p3/2 and Zn 2p1/2 are centered at about 1021.9 and 1044.6 eV, respectively, demonstrating the Zn is
a +2 valence state. The binding energy of O 1s is in good agreement with the literature values [46].
Both spectra are narrow and symmetrical and can be fitted with only one peak.
Fig. 3(a) shows the XRD pattern of AZO@MnO2, in which one diffraction peak can be indexed
to the birnessite-type MnO2 (JCPDS card No. 80-1098) in addition to those from ZnO and the
substrate.XRD revealed distinct yet broad peaks at 2θ = 12.2 which can be assigned to the (001) plane
of a crystalline birnessite-type MnO2 [47]. It is probable that the other diffraction peaks of the MnO2
nanosheets are too weak to be observed due to the strong and sharp diffraction peaks of the SS
substrate. The low intensity and broadening of the diffraction peak also suggest the small grain size
Int. J. Electrochem. Sci., Vol. 8, 2013 2319

and poor crystallinity of the MnO2, which can be confirmed by the TEM results. Fig. 3(b) shows the
Raman spectra of AZO@MnO2.

Figure 3. (a) XRD pattern and (b) Raman spectra of AZO@MnO2 hybrid core/shell arrays; (c, d)
FESEM images of the AZO@MnO2 hybrid core/shell arrays with a high uniformity and
regularity (Inset in Fig. 3(d) is an enlarged image of an individual nanostructure); and (e) cross-
sectional image of the AZO@MnO2 hybrid structure.

Three characteristic peaks centered at 506, 565, and 648 cm-1 are detected for the birnessite-
type MnO2. The Raman band at 648 cm-1 can be viewed as the symmetric stretching vibration (Mn-O)
of the MnO6 groups, and the band at 565 cm-1 is attributed to the (Mn-O) stretching vibration in the
basal plane of MnO6 sheets. Peaks centered around 332 and 437 cm-1 are two characteristic peaks in
the vibrational spectrum of single-crystalline ZnO. No observable signals of carbon were found when
the recording wavelength was extended up to 3000 cm-1, indicating the complete consumption of
carbon. Fig. 2(e) shows the Mn 2p XPS spectra of the AZO/ MnO2 hybrid structure. Two peaks of Mn
2P3/2 and Mn 2P1/2 centered at 642.4 and 654.3 eV are observed, with a spin-energy separation of 11.9
eV. The binding energies are in good accordance with previous reports of Mn 2P 3/2 and Mn 2P1/2 in
MnO2 [30], indicating the Mn ion in the product is present in the chemical state of Mn4+.
Fig. 3(c) and (d) show the FESEM images of the AZO@MnO2 hybrid core/shell architecture
on SS substrates. Highly branched and flaky MnO2 nanosheets were coated uniformly on the AZO
nanowire surfaces, forming a highly open and porous nanostructured surface morphology. This
Int. J. Electrochem. Sci., Vol. 8, 2013 2320

morphology greatly increases the packing density and utilization of active materials and results in a
high specific capacitance. Based upon the HR-FESEM observations, the thickness of nanosheet is
estimated to be about 3-5 nm (see Supplementary Information), consistent with a previous report [23].
Cross-sectional image of AZO@MnO2 obtained by the focused ion beam(FIB)-SEM technique is
shown in Fig. 3(e), confirming porous structures not only on the top surface but also within the arrays.
The open porous channels could increase the electrolyte-material contact and further facilitate the ionic
diffusion through the electrode, both contributing to a higher specific capacitance and better high rate
performances.

Figure 4. Microstructure characterization by TEM: (a) TEM image of an individual hybrid structure;
(b) an enlarged image of several MnO2 nanosheets from the hybrid structure; (c-e) HRTEM
images of MnO2 nanosheets. The red circled region in (c, d) indicates several dislocations.

Fig. 4 shows low-mag transmission electron microscopy (TEM) and high-resolution TEM
(HRTEM) images of the AZO@MnO2 nanowire arrays. High porous nanosheets uniformly cover the
core AZO nanowire (Fig. 4(a) and (b)), in agreement with the SEM results. The HRTEM images in
Fig. 4(c)-(e) show clear lattice fringes of polycrystalline structure with a spacing of ~0.67 nm
corresponding to the (001) crystallographic planes of the birnessite-type MnO2 [23]. The diffraction
pattern shown in the inset of Fig. 4(e) also confirms a polycrystalline structure of the MnO 2
Int. J. Electrochem. Sci., Vol. 8, 2013 2321

nanosheets. Dislocations are also noticed along the nanosheet direction (red circles in Fig. 4(c) and
(d)), indicating the poor crystallinity of the MnO2 nanosheets, which agrees well with the XRD results.

Figure 5. Electrochemical Performance of the AZO/MnO2 core shell electrodes: (a) CV curves at a
scan rate of 10 mV/s; (b) CV curves at 50-400 mV/s for theAZO@MnO2 hybrid electrode; (c,
d) Galvanostatic charge-discharge curves of the AZO@MnO2 and ZnO@MnO2 hybrid
electrodes, respectively; (e) specific capacitances as a function of different current densities;
and (f) specific capacitance increment as a function of different current densities.

The electrochemical capacitive performance of the AZO@MnO2 as well as the pure ZnO@
MnO2 nanowire arrays were evaluated with the cyclic voltammogram (CV) and galvanostatic charge-
discharge measurements. Fig. 5(a) shows the CV curves of the AZO@MnO2 and ZnO@MnO2
Int. J. Electrochem. Sci., Vol. 8, 2013 2322

hierarchical hybrid arrays recorded in a 1 M Na2SO4 aqueous solution at a scan rate of 10 mV/s. The
CV curve of AZO@MnO2 is quasi-rectangular and symmetric in shape without obvious redox peaks,
reflecting ideal pseudocapacitive behavior [48]. The pseudocapacitive electrochemical performance of
the AZO@MnO2 outperforms that of ZnO@MnO2 as referred from a more ideal CV profile and larger
CV integrated area. The specific capacitance (Csp) of the electrode can be calculated from CV curves
according to the following equation:

Q
C sp 
V  m (2)

where C (F/g) is the specific capacitance, m (g) is the mass of the total electrode materials (or
mass of the active materials), Q(C) is the average charge during the charging and discharging process,
and ΔV(V) is the potential window.
At a scan rate of 10 mV/s, a high specific capacitance of 213 F/g (based on total electrode
mass, ~355 F/g based on MnO2) was achieved from AZO@MnO2; while the value is 151 F/g for
ZnO@MnO2 under the same conditions of measurement. To further investigate the electrochemical
performances of AZO@MnO2 and ZnO@MnO2, higher rate capability experiments were carried out.
Fig. 5(b) shows the cyclic voltammograms (CV) of AZO@MnO2 measured at different sweep rates of
50, 100, 200 and 400 mV/s. The CV profiles retain a rectangular shape at all sweep rates without
obvious redox peaks, indicating again the ideal pseudocapacitive nature as well as suitability for high
rate operation of the AZO@MnO2 hybrid electrode. At a high scan rate of 400 mV/s, the average
specific capacitance was ~100 F/g, ~47% of that at 10 mV/s. This implies that even at higher scan
rates, considerable active materials can still be electrochemically utilized. For comparison, the cyclic
voltammograms of the ZnO@ MnO2 were measured at the same scan rates (see Supplementary
Information). It is noted that the integrated area of the AZO@MnO2 at the same scan rate is larger than
that of ZnO@MnO2, which suggests the AZO@MnO2 has a higher specific capacitance as well as
excellent rate capacitance properties.
Galvanostatic charge/discharge measurements were carried out on AZO@MnO2 and
ZnO@MnO2 electrodes in the potential range of 0-0.8V at different current densities. The results were
shown is Fig. 5(c) and (d), respectively. As can be seen from the constant current charge-discharge
curves, the discharge time of AZO@MnO2 electrode is substantially enhanced compared with
ZnO@MnO2 electrode and the charge/discharge curves for AZO@MnO2 electrode show more
symmetrical profiles than these of the ZnO@MnO2 electrode, a result of the enhancement of the
conductivity in the core supporting nanowires. The discharge specific capacitance can be calculated
from the discharge curves by the following equation:

It
C sp 
mV (3)
Int. J. Electrochem. Sci., Vol. 8, 2013 2323

Where Csp (F/g) is the specific capacitance, I is the discharging current, Δt is the discharging
time, ΔV is the potential window, and m (g) is the mass of the total electrode materials (or mass of the
active materials).
At a low current density of 2 A/g, the specific capacitances of AZO@MnO2 and ZnO@MnO2
are calculated to be about 275 (based on total electrode mass, ~458 F/g based on MnO2) and 210 F/g,
respectively. Fig. 5(e) shows the variation of the Csp value as a function of current densities for the
AZO@MnO2 and ZnO@MnO2 electrodes. It can be seen that the AZO@MnO2 electrode not only
delivers higher specific capacitances, but also maintain it at a high current density compared with the
ZnO@MnO2 electrode. As shown in Fig. 5(e), for AZO@MnO2 hybrid electrode, a specific
capacitance of 93.5 F/g (~35% retention) was retained as the rate changes from 2 to 60 A/g. While for
ZnO@MnO2 electrode, only 18.5 F/g (i.e., ~9% capacity retention) was achieved at a current density
of 60 A/g. An over 400% specific capacitance increment was achieved at a high current density of 60
A/g (Fig. 5(f)), indicating a greatly improved rate performance for the Al-doping and hydrogenation of
the ZnO as compared with pure ZnO nanowires.
AZO@MnO2 electrode exhibited comparable or superior performance to other MnO2-based
composite materials such as Ag-loaded manganese oxide nanosheets (272 F/g at 10 mV/s) [49], MnO2
nanoflower-CNTs composite arrays (199 F/g at a lower current density) [50], ultrafine MnO2 nanowire
network (279 F/g at 1A/g) [51], and graphene oxide-MnO2 nanocomposites (111 F/g at 1A/g) [52].
Very recently, He et al. [30] reported the synthesis of electrodeposited ZnO nanorod/MnO2 shell
composites, which exhibited a specific capacitance as high as 405 F/g at a scan rate of 10 mV/s.
The performance of the hybrid AZO/MnO2 is much higher than that of the pure manganese
oxide nano-sheet electrodes (90 F/g at a scan rate of 10 mV/s) [49]. In the present work, since
AZO@MnO2 and ZnO@MnO2 have almost the same surface morphologies, similar behavior in ion
diffusion is expected. Therefore, the enhanced electrochemical performance could be caused by the
improvement of conductivity in core-supporting nanowire material. The highly conductive AZO core
functions as an optimized electron-conducting pathway, which could support fast electron
transportation as required by high rate capability. By combining the characteristics of the two
components, fast ion and electron transfers are accelerated in the unique AZO@MnO2 hierarchical
architecture.
In aqueous electrolytes, the charge storage mechanism of MnO2 could be described by the
following reaction:

(MnO2)surface +M++e-  (MnO2-M+)surface (M =Li+, Na+, K+, or H3O+) (4)

It is reported that the charge storage is only involved the surface atoms of the MnO 2 crystallites
or at a very thin layer [53]. AZO@MnO2 exhibits a large specific surface area of electroactive MnO2
material, in which numerous active sites are available for the adsorption of Na+ and possible
intercalation/de-intercalation of Na+ [31]; hence a high specific capacitance could be expected.
Therefore, highly porous and accessible ultrathin nanosheet shell structure can enhance the
electrochemical utilization of active sites as well as enable fast and reversible faradic reactions by
shortening the ion diffusion path. It is noteworthy that the overall capacitance of the electrode is
Int. J. Electrochem. Sci., Vol. 8, 2013 2324

mainly contributed from active MnO2 component. For one reason, ZnO has a small capacity [28,30].
For another, since ZnO were coated with porous MnO2, electron transfer reaction (Faradaic reaction)
mainly occurs at the surface of the electrode, and core material could rarely take part in the charge-
storing process [26].

Figure 6. Ragone plot(power density vs. energy density) of the AZO@MnO2 and ZnO@MnO2 hybrid
electrodes.

Fig. 6 shows the Ragone plot (power density vs energy density) of the AZO@MnO2 and
ZnO@MnO2 electrodes. The power density and energy density are calculated from the following
equations:

C V 
1
E
2

2 (5)

E
P
t

Where E (Wh/kg). C (F/g), ΔV (V), t (s) and P (kW/kg) are the energy density, specific
capacitance, potential window of discharge, discharge time and power density, respectively. The
energy and power densities were calculated from charge-discharge curves at different current densities.
The energy-power performance of the AZO@MnO2 electrode is higher than that of the ZnO@MnO2
because of a higher specific capacitance. For AZO@MnO2, even at a high power density of
~30kW/kg, the energy density still reaches to be ~8.5 Wh/kg. At a lower power density of
Int. J. Electrochem. Sci., Vol. 8, 2013 2325

~0.85kW/kg, the energy density reaches as high as ~24 Wh/kg. While for pure ZnO@MnO2, the power
density can still reach ~30 kW/kg, but the energy density is as low as ~1.7 Wh/kg; at a lower power
density of ~0.80kW/kg, the energy density drops to ~18 Wh/kg. The AZO@MnO2 hybrid electrode
delivered a high energy density of 11.7 Wh/kg at a power density of ~12 Wh/kg, which is about 2.5
times larger than that of the pure ZnO@MnO2. The comparison suggests that for AZO@MnO2
electrode, higher energy densities could be attained while still maintaining the characteristic of high
power density.

Figure 7. The specific capacitance as a function of cycle number at 10 A/g of the AZO@MnO2 hybrid
electrode. Inset shows the last 10 charge-discharge curve of the hybrid electrode.

To evaluate the durability of the AZO@MnO2 hybrid electrode, cycling capability test was
carried out at a high charge-discharge current density of 10 A/g using the constant current
galvanostatic charge/discharge cycling technique in the potential window ranging from 0 to 0.8 V. Fig.
7 shows the specific capacitance retention of the AZO@MnO2 hybrid electrode as a function of
charge/discharge cycling numbers. The specific capacitance increases slightly at first and then
decreases less than 3% in capacitance after 2000 charge-discharge cycles. The cycling stability of
AZO@MnO2 hybrid electrode is superior to pure MnO2 and MnO2-GO composites [51]. The last 10
cycles (inset in Fig. 7) exhibit highly symmetric charge/discharge characteristics, confirming the
excellent long-term cyclability of the hybrid electrode. Excellent cycling stability was also
Int. J. Electrochem. Sci., Vol. 8, 2013 2326

demonstrated on nickel hydroxidenitrate nanoflakes-coated ZnO nanowire arrays [28], proving the
good durability and integrity of the hierarchical architecture.

4. CONCLUSIONS

In summary, Al-doped and hydrogenated ZnO nanowire arrays were used as supporting
backbone infrastructures in fabricating AZO@MnO2 hybrid core/shell electrode. The unique
architecture of AZO@MnO2 hybrid electrode offers high surface area, fast ion transportation, and
good electronic conductivity, resulting in superior electrochemical performances (high specific
capacitances, excellent rate capability and cycle stability). The hybrid AZO/MnO2 core/shell electrode
displays simultaneously-enhanced energy and power densities as compared with the pure ZnO/MnO2
electrode. The extraordinary supercapacitor performance and the cost-effective and scalable synthesis
approach suggest that AZO@MnO2 hybrid electrode could be considered as promising electrode
material for supercapacitor applications. Taking advantage of both highly electrochemical active MnO2
nanosheets and highly conductive core nanowires as electron conducting pathways, the doping and
hydrogenation approach reported here can be applied in the fabrication of other promising
TOx@MnO2 (T = Ti, Sn, Fe, W, Cu, Ag, Ir, Ru, etc.) core/shell electrodes for further improvement of
the electrical conductivity and capacitive performance for electrochemical energy storage applications.

ACKNOWLEDGEMENTS
This work was supported by a NSF career award under the Award number of DMR 1151028. The
author Mingpeng Yu thanks for the financial support from China Scholarship Council (CSC File No.
2010646040).

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Support information:

The ZnO seed layers (about 20 nm in thickness) were coated on the stainless steel substrate by
sputtering method. ZnO nanowire arrays were grown by immersing the seeded stainless steel substrate
into in a precursor solution containing 25 mM zinc nitride and 25mM hexamethylenetetramine
(HMTA) at 85 °C for 5 h in a 45 mL teflon-lined stainless steel autoclave (Parr, 4049). As the doping
source, aluminum nitrate nonahydrate (Al(NO3)3 · 9H2O) was added in the precursor solution. Al
doping concentration (the atom ratio of Al to Zn) was chosen to be 20 at.%.

Figure S1. Typical TEM and HRTEM images as well as electron diffraction pattern of a single AZO
nanowire. The HRTEM image confirms the single-crystal structure of the AZO nanowire and
also demonstrates the lattice spacing of 0.52 nm in accordance with the c lattice constant of
ZnO, indicating that the nanowire growth direction is along the c axis.

Figure S2. HR-FESEM observation of a single piece of MnO2 nanosheet.

Int. J. Electrochem. Sci., Vol. 8, 2013 2329

Figure S3. CV curves at 50-400 mV/s for ZnO@MnO2 electrode.

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