Manganese Oxide-Based Materials

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Cite this: Chem. Soc. Rev., 2011, 40, 16971721
CRITICAL REVIEW
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Manganese oxide-based materials as electrochemical

supercapacitor electrodes
Weifeng Wei,ab Xinwei Cui,a Weixing Chena and Douglas G. Ivey*a
Received 28th September 2010
DOI: 10.1039/c0cs00127a
Electrochemical supercapacitors (ECs), characteristic of high power and reasonably high
energy densities, have become a versatile solution to various emerging energy applications.
This critical review describes some materials science aspects on manganese oxide-based materials
for these applications, primarily including the strategic design and fabrication of these electrode
materials. Nanostructurization, chemical modication and incorporation with high surface
area, conductive nanoarchitectures are the three major strategies in the development of
high-performance manganese oxide-based electrodes for EC applications. Numerous works
reviewed herein have shown enhanced electrochemical performance in the manganese oxide-based
electrode materials. However, many fundamental questions remain unanswered, particularly with
respect to characterization and understanding of electron transfer and atomic transport of the
electrochemical interface processes within the manganese oxide-based electrodes. In order to fully
exploit the potential of manganese oxide-based electrode materials, an unambiguous appreciation
of these basic questions and optimization of synthesis parameters and material properties are
critical for the further development of EC devices (233 references).
1. Introduction
Sustainable and renewable energy resources are being intensively
pursued owing to the diminishing supply of fossil fuels and
climate change. Consequently, rapid growth in renewable
a
Department of Chemical and Materials Engineering,

University of Alberta Edmonton, Alberta, Canada T6G 2G6.
E-mail: doug.ivey@ualberta.ca; Fax: +1 780-492-2881;
Tel: +1 780-492-2957
b
Department of Materials Science and Engineering,
Massachusetts Institute of Technology, Cambridge, MA 02139, USA
energy production from sun and wind, as well as the development of electric vehicles (EVs) or hybrid electric vehicles
(HEVs) with low CO2 emissions, is occurring. Since renewable
sources from sun and wind generally have on-peak and o-peak
load variations and EVs/HEVs have a driving range of
150200 miles before charging is required, electrochemical
energy storage systems such as rechargeable batteries and electrochemical capacitors (ECs) are receiving increasing consideration.1
A Ragone plot (Fig. 1) illustrates power density against
energy density for the most important electrochemical energy
storage systems.2,3 ECs, with a combination of high power and
Weifeng Wei is currently a

postdoctoral researcher in
the Department of Materials
Science
and
Engineering
at the Massachusetts Institute
of Technology (MIT). He
received his PhD in Materials
Engineering from the University
of Alberta (2009). His research
interests include materials
development
for
electrochemical energy storage devices
(rechargeable batteries and
supercapacitors).
Weifeng Wei
This journal is
The Royal Society of Chemistry 2011
Xinwei Cui
Xinwei Cui received a Bachelor

of Science degree in Materials
Engineering from the University Science and Technology
Beijing in 2005 and a PhD in
Materials Engineering from
the University of Alberta in
2010. He is currently a research
associate in the Department of
Chemical
and
Materials
Engineering at the University
of Alberta. His research
focuses on nanostructured
materials, particularly carbon
nanomaterials for applications in electrochemical energy
storage and conversion.
Chem. Soc. Rev., 2011, 40, 16971721
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The pioneering work on the pseudocapacitive behavior of

manganese oxide in an aqueous solution was published in 1999
by Lee and Goodenough.13,14 This was followed by several
studies to establish the charge storage mechanism in manganese
oxide electrodes. Pseudocapacitive (Faradic) reactions
occurring on the surface and in the bulk of the electrode are
the major charge storage mechanisms for manganese oxides.
The surface Faradaic reaction involves the surface adsorption
of electrolyte cations (C+ = H+, Li+, Na+ and K+) on the
manganese oxide:15,16
(MnO2)surface + C+ + e 2 (MnOOC)surface
(1)
The bulk Faradaic reaction relies on the intercalation or

deintercalation of electrolyte cations in the bulk of the
manganese oxide:15,16
MnO2 + C+ + e 2 MnOOC
Fig. 1 Ragone plot (specic power vs. specic energy) for various
electrochemical energy storage devices. (Reproduced from ref. 2;
reprinted with permission. Copyright 2008, Macmillan Publishers
Limited.)
reasonably high energy density, are a versatile solution to a

variety of emerging energy applications. The energy stored in
the ECs is either capacitive or pseudocapacitive in nature. The
capacitive (non-Faradaic) process is based on charge separation at the electrode/electrolyte interface, while the pseudocapacitive (Faradaic) process relies on redox reactions that
occur in the electrode materials. The most widely used active
electrode materials are carbon, conducting polymers and
transition metal oxides.414 Among these electrode materials,
manganese oxides, characterized by high specic capacitance
and their low-cost, abundance and environmentally friendly
nature, have attracted signicant interest as active electrode
materials for ECs.
Weixing Chen is an associate

professor in the Department
of Chemical and Materials
Engineering at the University
of Alberta. He is interested in
fabricating carbon nanotube
arrays and their applications,
in addition to corrosion and/
or environmentally induced
cracking of materials used in
energy and petrochemical
processing industries.
Weixing Chen
1698
Chem. Soc. Rev., 2011, 40, 16971721
(2)
It is noted that, in both charge storage mechanisms, a redox

reaction between the III and IV oxidation states of Mn ions
occurs. In general, hydrated manganese oxides exhibit specic
capacitances within the 100200 F g 1 range in alkali salt
solutions, which are much lower than those for RuO2 ECs.
Thus far, further advancements in current MnO2-based supercapacitors are constrained by MnO2 electrode material limitations with limited specic capacitance (low energy density),
lack of structural stability and long-term cyclability, and low
rate-capacity.
The improvement pursued in active materials mainly concerns
high reversible capacitance, structural exibility and stability,
fast cation diusion under high chargedischarge rates,
and environmental friendliness. As a transition metal
element, manganese can exist as a variety of stable oxides
(MnO, Mn3O4, Mn2O3, MnO2)17,18 and crystallize in various
types of crystal structures, as shown in Fig. 2 and Table 1.1929
Associated with a wide diversity of crystal forms, defect
chemistry, morphology, porosity and textures, manganese
oxides exhibit a variety of distinct electrochemical properties.
These structural parameters play a crucial role in determining
Douglas Ivey is a professor in

the Department of Chemical
and Materials Engineering at
the University of Alberta and
director of the Alberta Centre
for Surface Engineering and
Science (ACSES). He received
his PhD in Engineering Materials from the University of
Windsor (Canada) in 1985.
His research focuses on
applying high resolution microstructural
characterization
techniques to understanding
the relationships between
Douglas G. Ivey
materials structure, properties
and processing. Recent work has focused on developing electrochemical techniques to deposit thin lms and thicker coatings for
a wide range of potential applications, from microelectronics to
MEMS to fuel cells to supercapacitors.
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Fig. 2 Schematic representation of the crystal structure of manganese oxides. (a) Rock salt; (b) spinel (Mn3O4); (c) bixbyite (Mn2O3);
(d) pyrolusite b-MnO2 (rutile-type) (note the single chains of edge-sharing octahedra); (e) ramsdellite (diaspore-type) ([MnO6] octahedra form
innite double layers); (f) phyllomanganate (birnessitebuserite family of layered MnO2). In this idealized representation there are alternate layers
of full and empty octahedral sites. (2df, adapted from ref. 36, reprinted with permission. Copyright 2006, The Electrochemical Society.)
Crystal structure of manganese oxides1929
Table 1
Type
Crystal structure
Description
MnO
Mn3O420
Rock salt, Fm3m

Tetragonal spinel, I41/amd
Mn2O321 (bixbyite)
a-MnO222 (psilomelane)
Body-centered cubic, Ia3

Monoclinic, A2/m
b-MnO223 (pyrolusite)
Rutile structure, P42/mnm
b-MnO224 (ramsdellite)
Pbnm
Face centered cubic (FCC) lattice with a 6 : 6 octahedral coordination.

Metal cations occupy 1/8 of the tetrahedral sites and 1/2 of the
octahedral sites and there are 32 oxygen anions in the FCC unit cell.
Body-centered cubic (BCC) unit cell with 16 formula units per unit cell
Cross-linking of double or triple chains of the [MnO6] octahedra,
resulting in two-dimensional tunnels within the lattice.
Rutile structure with an innite chain of [MnO6] octahedra sharing
opposite edges; each chain is corner-linked with four similar chains.
Closely related to rutile except that the single chains of edge-sharing
octahedra are replaced by double chains.
An irregular intergrowth of layers of pyrolusite and ramsdellite.
Dierent from g-MnO2 only in crystallite size and the concentration
of microdomains of pyrolusite within the ramsdellite matrix.
Layered structure, containing innite two-dimensional sheets
of edge-shared [MnO6] octahedra.
Hexagonal close packing of anions, with Mn4+ statistically distributed
over half the available octahedral interstices.
19
25,26
g-MnO2
Z-MnO2
(nsutite)
d-MnO227,28 (phyllomanganate)
Birnessite, R3m
e-MnO229
Defective NiAs, P63/mmc
and optimizing the electrochemical properties when manganese

oxides are applied as electrode materials. Investigation of the
inuence on these characteristics of manganese oxides on
capacitor performance is the basis of a rational design of improved
electrode materials. Extensive eorts have been dedicated to adjust
synthesis conditions to obtain manganese oxides with desirable
morphologies, defect chemistry (cation distributions and oxidation states) and crystal structures to improve the subsequent
capacitance and power characteristics.3037
The capacitance of thick MnO2 electrodes is ultimately
limited by the poor electrical conductivity of MnO2. On the
other hand, EC device performance using a planar ultrathin
conguration is restricted because of low mass loading. In
this case, incorporation of other metal elements into MnO2
compounds has also been extensively studied in recent years
to enhance their electrical conductivity and charge-storage
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capability. The chemical modication of MnO2 electrodes

can be generally divided into two categories: one is mixed
oxide electrodes containing other transition metal elements,
such as Ni, Cu, Fe, V, Co, Mo and Ru.11,3843 The other type
of a modied MnO2 electrode was realized through doping
with small amounts of other metallic elements such as
Al, Sn and Pb.4446 The corresponding electrochemical
properties indicate that the manipulation of defect chemistry
by chemical modication has signicant inuence on the
electronic conductivity and, in turn, on the specic capacitance
and rate capacity.
Another method to compensate for the poor electrical
conductivity of thick MnO2 electrodes is to deposit a thin
MnO2 layer on the surface of a porous, high surface area, and
electronically conducting structure, which can provide good
electrochemical performance with high mass-loading of the
Chem. Soc. Rev., 2011, 40, 16971721
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MnO2 phase. The porous architectures could be carbon

nanofoams, templated mesoporous carbon, nanographite,
and nanotube assemblies. In such a hybrid electrode conguration, the carbon substrates act as highly conductive current
collectors, the interconnected porosity serves as a continuous
pathway for electrolyte diusion, and the nanoscopic active
MnO2 phase shortens solid-state transport distances for ions
into the oxide materials.47 Recent eorts to integrate carbon
and MnO2 have primarily focused on depositing nanoscale MnO2 onto carbon nanotubes by using a variety of
approaches, including physical mixing of the components,48
thermal decomposition,49 chemical deposition using precursors
such as permanganate,50,51 and electrochemical deposition.52,53
In addition to their poor electrical conductivity, mechanical
issues such as low structural stability and exibility and
electrochemical dissolution of active materials exist for
MnO2 electrodes, resulting in degraded long-term electrochemical cyclability. To address electrochemical dissolution,
a self-limited growth process based on the electropolymerization of o-phenylenediamine has been developed.54,55 The
resulting polymer conformally coats the oxide nanoscale network, serving as an eective barrier to the electrolyte thereby
protecting the underlying MnO2 nanoarchitecture from chemical
dissolution. The underlying metal oxide remains electrochemically accessible but signicant reduction in conductivity is
observed.55 Many eorts have also been attempted to incorporate
conductive polymers (polyaniline, polypyrrole and polythiophene)
and their derivatives to get mixed MnO2polymer composite
electrodes with desirable morphologies.5659 The excellent
electronic conductivity, high stability, and mechanical exibility
of applied conductive polymers enable improved electrochemical and mechanical properties for MnO2polymer composite electrodes for ECs.59
Manganese oxide-based electrodes, either fabricated as a
single nanostructured component with desirable physicochemical
features or assembled with conductive polymers and porous
carbon architectures, open new possibilities for the development of advanced ECs. The strategies can be generalized as the
following options:
1. Chemical and structural modication of manganese oxide
materials to introduce more electrochemically active sites for
the redox reaction between the Mn(III) and Mn(IV).
2. Shortening of the transport path length for both
electrons and cations by using porous, high surface area,
and electronically conducting carbon architectures.
3. Addressing of the low structural stability and exibility
and electrochemical dissolution of active materials through
application of conductive polymers in manganese oxide
materials.
There are some reviews that cover dierent topics in
the development of ECs;3,6066 however, to the best of our
knowledge, none are dedicated to the development of
manganese oxide-based electrochemical supercapacitors. This
paper categorizes and reviews the most important related
works and achievements for manganese oxide-based ECs
published in the last ten years. Current challenges and future
strategies will be discussed. Herein, we focus on the materials
science of manganese oxides and manganese oxide-based
composites used as electrodes in ECs. Some other important
1700
Chem. Soc. Rev., 2011, 40, 16971721
aspects such as device engineering or electrolyte development

are not included in this work.
2. Manganese oxide electrodes

2.1 Powder electrodes
2.1.1 Amorphous MnO2 powder electrodes. In the rst
study on the capacitive behavior of manganese dioxide published
in 1999 by Lee and Goodenough, amorphous hydrated
manganese dioxide powders were prepared by reacting
KMnO4 with Mn(CH3COO)2 in water through the following
reaction:13,14
Mn(VII) + 3/2Mn(II) - 5/2Mn(IV)
(3)
It was found that the amorphous hydrated MnO2 powder

electrodes exhibited ideally capacitive behavior in KCl, NaCl,
and LiCl aqueous solutions. This was followed by several
studies that used similar KMnO4 reducing procedures with
dierent reducing agents, including MnSO4,15,30,67 potassium
borohydride,68 sodium dithionite,68 sodium hypophosphite
and hydrochloric acid,68 aniline,69 and ethylene glycol32 to
make hydrated MnO2 powders. In addition to water-based
procedures, organic solvent-assisted reduction of KMnO4
was investigated. Typical cases are reduction of KMnO4 in
an AOT/iso-octane solution,70 a H2O/CCl4 interface, and a
ferrocene/chloroform solution.31,71 In the rst case, surfactant
sodium bis(2-ethylhexyl)sulfosuccinate (AOT) was used as
both the dispersant and reducing agent. KMnO4 aqueous
solution was dispersed in iso-octane by AOT to form nano
droplets of the water phase, and then KMnO4 was reduced by
AOT.70 The other two processes involved interfacial reactions
occurring at the aqueous/organic interface. The formation
of MnO2 at the interface of aqueous KMnO4/ferrocene in
chloroform can be described as follows. With the presence of
sodium dodecylsulfate (SDS), the micelles containing KMnO4
were formed and arranged at the aqueous/organic interface.
Ferrocene molecules contacted the permanganate at the core
of the micelles and redox took place at the interface to form
MnO2 particles in the micelles.31
The as-prepared hydrated MnO2 powders are generally
amorphous or poorly crystalline in nature. A representative
X-ray diraction (XRD) pattern for as-prepared hydrated
MnO2 powders is depicted in Fig. 3a.32,69 The hydrated
MnO2 powders maintain their amorphous characteristics up
to 300 1C (Fig. 3b and c), whereas a-MnO2 with a tunnel
structure matching JCPDS 44-0141 appears for samples
heat treated at temperatures higher than 400 1C for 3 h
(Fig. 3df).69 Similar structural evolutions during heat treatment were also observed in other studies. For instance,
Belanger et al. demonstrated decomposition of a-MnO2 into
a-Mn2O3 (bixbyite-C, Ia3 space group) at 400 1C, with the
well-crystallized a-Mn2O3 becoming the main phase at
600 1C.30 Devaraj and Munichandraiah also showed the structural evolution from a-MnO2 (as-prepared at B400 1C) to
a-Mn2O3 (500800 1C) and then to Mn3O4 (900 1C).72
Along with the structural evolution occurring during heat
treatment, the morphology and chemistry of the hydrated
MnO2 powders change signicantly. Fig. 4 shows SEM images
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Fig. 3 XRD patterns of as-prepared and annealed MnO2 samples.

(a) Dried in air and annealed at 50 1C, (b) 200 1C, (c) 300 1C,
(d) 400 1C, (e) 500 1C, and (f) 600 1C for 3 h in air. (Reproduced
from ref. 69, reprinted with permission. Copyright 2008, The Electrochemical Society.)
Fig. 4 SEM images of MnO2 (a) as prepared and dried at 50 1C in

air (inset shows energy-dispersive X-ray spectrum) and annealed at
(b) 200 1C, (c) 300 1C, (d) 400 1C, (e) 500 1C, and (f) 600 1C for 3 h in
air. Arrows in (c) indicate initiation of nanorods. (Reproduced from
ref. 69, reprinted with permission. Copyright 2008, The Electrochemical Society.)
of the morphology of MnO2 annealed at dierent temperatures.69

Amorphous MnO2 exhibits highly clustered granules of
varying size between ve and tens of nanometres, as shown
in Fig. 4a. As the annealing temperature is increased to 300 1C,
gradual growth of nanorods begins (Fig. 4c and d). Upon
further heating to 500 and 600 1C, well-dened nanorods of length
500750 nm and diameter 50100 nm are seen (Fig. 4e and f).32,69
Note that the morphological change from particles to nanorods is
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also evident in the hydrated MnO2 powders prepared through

a microemulsion method.72 Through X-ray photoelectron
spectroscopy (XPS) analysis, it has been well established that
the as-prepared MnO2 powders contain a signicant amount
of hydrated content (hydrated trivalent MnOOH and residual
structural water).15,32 The hydrated content in the MnO2
powders was reduced considerably by increasing the annealing
temperature.32 At the same time, the specic surface area of
the MnO2 powders declines dramatically with increasing
annealing temperature and holding time, as shown in
Table 2.32,72
The electrochemical properties of the hydrated MnO2
powder electrodes are evaluated using cyclic voltammetry
(CV), galvanostatic chargedischarge, and electrochemical
impedance spectroscopy (EIS). The specic capacitance C
(F g 1) of the MnO2 powder electrodes is determined by
obtaining the voltammetric charge (Q) from the cyclic voltammograms or the galvanostatic chargedischarge curves. Then Q is
divided by the mass of the active materials in the electrodes (m)
and the width of the potential window DE.
C = Q/(mDE)
(4)
The specic capacitance of the hydrated MnO2

powder electrodes is rather sensitive to their microstructure
(surface area) and hydrated content. An increase in the surface
area will enhance the specic capacitance of the amorphous
MnO2 powder electrodes.15 As illustrated in Table 2, it was
found that the surface area and specic capacitance decreased
slightly when heated to 300 1C.32,72 For MnO2 powders
prepared through a microemulsion method, a dramatic
decrease in the surface area and specic capacitance occurred
for samples annealed at 300 and 400 1C, together with a
structural change.32,72 For MnO2 powders prepared through
reduction with ethylene glycol, however, a rapid reduction in
surface area and specic capacitance occurred at 500 1C, which
was associated with an a-MnO2 to Mn2O3 phase transformation. Assuming that specic capacitance is closely related to
surface area, secondary pores, and water content, which
supports the proposed surface eect for the operating mechanisms of an electrode material for supercapacitors, these
properties decrease with increasing temperature.
2.1.2 Crystalline MnO2 powder electrodes. As described
above, there are many types of crystal structures occurring in
manganese oxides, whose structural frameworks consist of
MnO6 octahedra sharing vertices and edges. The stacking of
the MnO6 octahedra enables the building of 1D, 2D, or 3D
tunnel structures, which can be seen in Fig. 2. The dierent
crystal structures can be described by the size of the tunnel
determined by the number of octahedra subunits (n m), as
indicated in Fig. 2. The tunnels can be lled with either water
molecules or cations such as Li+, Na+, K+, and Mg2+, so the
crystalline manganese oxides are expected to demonstrate
interesting electrochemical properties in a mild aqueous
electrolyte.
The rst systematic study comparing the capacitive properties
of MnO2 powders with various crystal structures was published
by Brousse et al. in 2006.36 The MnO2 powders were prepared
through co-precipitation and solgel techniques under
Chem. Soc. Rev., 2011, 40, 16971721
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Table 2
Structure type, surface area (m2 g 1), and specic capacitance (F g 1) for MnO2 at dierent temperatures32,72
MnO2 (microemulsion)
As-prepared
200 1C
300 1C
400 1C
500 1C
600 1C
a
MnO2 (reducing with ethylene glycol)
Structure
Surface area,
SBETa/m2 g 1
Capacitance/F g
d-MnO2
d-MnO2
d-MnO2
a-MnO2
a-MnO2
a-MnO2
230
212
194
36
34
22
250
225
207
85
73
61
Structure
Surface area,
SBETa/m2 g 1
Capacitance/F g
a-MnO2
a-MnO2
a-MnO2
a-MnO2
Mn2O3
Mn2O3
145
146
119
16
8
1
300
260
254
245
70
40
The surface area of MnO2 powders was measured using BrunauerEmmettTeller (BET) technique.
Table 3
Relationship between the crystal structure, BET surface area, and specic capacitance36
Compound
Structure
SBET/m2 g
co-MnO2
Ambigel H2SO4
Ambigel H2O
l-MnO2
g-MnO2
b-MnO2
Birnessite H2O
Birnessite H2SO4
Birnessite
a-MnO2
a-MnO2
a-MnO2
l-MnO2
g-MnO2
b-MnO2
Birnessite d-MnO2
Birnessite d-MnO2
Birnessite d-MnO2
200
208
8
35
41
1
17
89
3
dierent synthesis conditions to achieve a variety of crystal

structures such as a-, b-, d-, g-, and l-type crystal structures.
The relationship between the crystal structure, BET surface
area and specic capacitance can be seen in Table 3.36 It was
revealed that the capacitance of the dierent materials depends
strongly on the crystalline structure, i.e., the size of the tunnels
that limits the intercalation of cations.36 Birnessite d-MnO2
with a 2D tunnel structure doped with potassium has relatively
high specic capacitance values (110 F g 1) even with moderate
BET surface area (17 m2 g 1). 1D tunnel structures, such as
b- or g-MnO2, provide only a pseudoFaradaic surface
capacitance that is closely related to the BET surface area of
the crystalline materials. 3D tunnel structures containing
l-MnO2 show intermediate electrochemical performance
between birnessite and 1D tunnel structures.36
More recently, another systematic study dealing with the
eects of crystallographic forms of MnO2 on the electrochemical performance was conducted by Ghodbane et al.37
A series of MnO2 allotropic phases were prepared. The 1D
structures included pyrolusite, ramsdellite, cryptomelane,
Ni-doped todorokite (Nitodorokite), and OMS-5. The 2D
and 3D structures were birnessite and spinel, respectively.37
Fig. 5 illustrates the relationship between the crystal structure,
BET surface area, and specic capacitance.37 It was discovered
that the 3D-type spinel showed the highest capacitance, followed
by the 2D layer birnessite sample. For the 1D tunnel group, a
larger cavity corresponded to a larger capacity.37 The comparison of the BET surface area and electrochemical results
also showed that the specic surface area has a limited impact
on the capacitance of MnO2 electrodes. Charge storage in
prepared MnO2 materials is mainly Faradaic.37 The specic
capacitance correlates with the ionic conductivity of the MnO2
powder, which is clearly related to the crystallographic
microstructure.37
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Chem. Soc. Rev., 2011, 40, 16971721
C/F g
150
150
125
70
30
5
110
105
80
Scan rate/mV s
5
5
5
5
5
5
5
5
5
Electrolyte
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.1
M
M
M
M
M
M
M
M
M
K2SO4
K2SO4
K2SO4
K2SO4
K2SO4
K2SO4
K2SO4
K2SO4
K2SO4
Fig. 5 Comparison of the specic capacitance, ionic conductivity and

BET surface area of various MnO2 structures. (Reproduced from
ref. 37, reprinted with permission, copyright 2009, American Chemical
Society.)
Hydrothermal or solvothermal synthesis is an interesting

technique to prepare materials with dierent nanoarchitectures
including nanoparticles, nanorods, nanowires, nano-urchins,
and nanotubes by properly choosing the reaction temperature
or time, or the active ll level or solvent used for the reaction.
For instance, Subramanian et al. reported a hydrothermal route
based on aqueous solutions of MnSO4H2O and KMnO4.73,74
Through varying the hydrothermal time, evolution from a
distinct plate-like morphology to nanorods was observed in
as-prepared MnO2 nanocrystals, as shown in Fig. 6a and b.73
Xu et al. reported another simple hydrothermal process, based
on KMnO4, sulfuric acid and Cu scraps, for preparing
a-MnO2 hollow spheres and hollow urchins.75 The hollow
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Fig. 6 Crystalline MnO2 with plate-like (a), nanorod (b), hollow

sphere, urchin (c), cubic (d), nanowire (e), and lamellar (f) morphologies prepared from hydrothermal processes. (a and b, reproduced
from ref. 73, reprinted with permission, copyright 2005, American
Chemical Society; c reproduced from ref. 75, reprinted with
permission, copyright 2007, American Chemical Society; d and e,
reproduced from ref. 78, reprinted with permission, copyright 2008,
American Chemical Society; f, reproduced from ref. 77, copyright
2010, Elsevier Ltd.)
sphere or urchin structured a-MnO2 materials possess a highly

loose, mesoporous cluster structure consisting of thin plates or
nanowires (Fig. 6c) and exhibit enhanced rate capacity and
cyclability.75 Similar morphologies were also observed in
a-MnO2 prepared from KMnO4 and nitric acid-containing
reactants, and in a-MnO2 and e-MnO2 nanostructures
prepared at a low temperature (110 1C).76,77 A modied
hydrothermal process based on Mn(CH3COO)24H2O and
K2S2O8 was also introduced to synthesize Mn3O4 and
MnOOH single crystals utilized as EC electrode materials.78
The morphology and crystal structure of the Mn3O4 and
MnOOH single crystals are shown in Fig. 6d and e.78
Similarly, single crystalline Mn3O4 nano-octahedrons were
synthesized by an ethylenediaminetetraacetic acid disodium
salt (EDTA-2Na) assisted hydrothermal route.79 More recently,
lamellar birnessite d-MnO2 with dierent interlayer spacings
was prepared by hydrothermal synthesis, as shown in Fig. 6f.
The microstructure was found to be controlled by changing
the pH value of the initial reaction system.77
In addition to the hydrothermal technique, low temperature
reduction processes were also developed to prepare crystalline
MnO2 powders. Rod-shaped MnO2, consisting of both a- and
g-MnO2, was synthesized under high viscosity conditions
at a temperature of 65 1C.80 Similar rod-shaped MnO2 with
a d-type structure was also prepared through a room temperature precipitation route based on a MnSO4 + K2S2O8 solution,
as shown in Fig. 7a.81 Monodisperse manganese oxide owerlike nanostructures have been prepared facilely at 40 1C and
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Fig. 7 Crystalline MnO2 with various morphologies prepared from

low temperature reduction processes. (a) Reproduced from ref. 81,
reprinted with permission, copyright 2009, American Chemical
Society; (b) reproduced from ref. 83, copyright 2010, Elsevier Ltd.;
(c) reproduced from ref. 87, copyright 2010, Elsevier Ltd.; (d) reproduced
from ref. 86, copyright 2010, Elsevier Ltd.
ambient atmosphere using KMnO4 and formamide

(HCONH2).82 Low-cost layered manganese oxides with the
rancieite structural type (Fig. 7b) were prepared by reduction of KMnO4 or NaMnO4 in acidic aqueous medium at
temperatures of 20 1C, 60 1C or 100 1C for 10 h, followed by
successive proton- and alkali-ion exchange reactions.83 Sonoor microwave sources were also introduced into the synthesis
process of crystalline MnO2 powders.84,85 A typical nanobeltlike morphology can be observed in the MnO2 powders
prepared by a microwave-assisted process.86 Template-assisted
solgel is another eective way to prepare crystalline MnO2
powders with distinct morphologies. Through this technique,
Wang et al. synthesized MnO2 nanowires or nanorods with a
hollandite type a-MnO2 structure, as shown in Fig. 7c.87
Moreover, a solution combustion technique based on
Mn(NO3)2 and C2H5NO2 was developed to obtain plate-like
and spherical e-MnO2 particles. A representative SEM image
of the morphology of plate-like e-MnO2 is shown in Fig. 7d.86
Table 4 summarizes the synthesis conditions, physicochemical
features, and specic capacitances of crystalline MnO2 prepared
with dierent techniques. Highly scattered results were reported
on the specic surface area and capacitance of nanocrystalline
MnO2 powder electrodes. An unambiguous relationship
among the synthesis conditions, physicochemical features,
and specic capacitance has still not been obtained.
2.1.3 Summary of amorphous and crystalline MnO2 powder
electrodes. Dierent MnO2 powders, prepared by chemical
co-precipitation, hydrothermal/sonothermal, solgel and solution
combustion techniques, have been investigated as possible
active electrode materials for electrochemical capacitors in
mild aqueous electrolytes. For the amorphous and crystalline
MnO2 compounds, a large variation in specic capacitance
values was reported. In the literature one can nd that
many factors inuence the charge storage process, including
porosity, morphology, defect chemistry (cation distributions
Chem. Soc. Rev., 2011, 40, 16971721
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Table 4
Synthesis conditions, physicochemical features, and subsequent specic capacitance of crystalline MnO2
Technique
Synthesis conditions
Morphology
Structure
SBET/m2 g
Hydrothermal
MnSO4H2O+ KMnO4,
140 1C73,74
KMnO4 + sulfuric acid and
Cu scraps, 110 1C75
KMnO4 + nitric acid, 110 1C76
MnSO4 + K2S2O8 + sulfuric acid,
110 1C88
Mn(CH3COO)2 + K2S2O8, 120 1C78
a-NaMnO2 + nitric acid, 120 1C77
KMnO4 + MnCl2 + PG + PAM,
65 1C80
MnSO4 + K2S2O881
Plate-like, nanorods
a-MnO2
100150
Hydrothermal
Hydrothermal
Hydrothermal
Hydrothermal
Hydrothermal
High viscosity
process
Room temperature
precipitation
Low temperature
reduction
Low temperature
reduction
Sonochemistry
Microwave-assisted
emulsion
Solgel process
KMnO4 + formamide, 40 1C
82
52108
80119
86152 (5 mV s 1)
46120 (5 mV s 1)
Cubes and nanowires Mn3O4, MnOOH

Lamellar
d-MnO2
Rod-shaped
a-MnO2, g-MnO2
B170 (500 mV s 1)
241 (2 mA cm 2)
389 (10 mV s 1)
Rod-shaped
d-MnO2
201
Nanoower
Cubic MnO2 (Fd3m) 225.9
121.5 (1000 mA g 1)
Rancieite structure
11206
17112 (2 mV s 1)
g-MnO2
118344
d-MnO2
277 (0.2 mA cm 2)
Nanorods
g-MnO2
317 (100 mA g 1)
Plate-like
e-MnO2
2343
71123
(1000 mA g 1)
Thin-lm MnO2 electrodes
Because of the interest for more fundamental studies and

potential applications as micro-scale energy storage systems
such as integrated devices, thin lm or MnO2 coating electrodes
have been intensively explored recently. In this case, a
manganese oxide thin layer with desirable physical features
is directly assembled on a current collector through a variety
1704
Chem. Soc. Rev., 2011, 40, 16971721
Hollow spheres,
a-MnO2
hollow urchins
Urchin-like
a-MnO2
Urchin-like, clew-like a-MnO2, e-MnO2
and oxidation states), crystal structure, and residual water

content. It should be pointed out that there is still no standard
uniform structure and morphology available for MnO2
materials. A comparison between electrodes consisting of
various kinds of MnO2 powders is rather dicult since
MnO2 powders produced under dierent conditions exhibit
dierent structures and properties. It is believed that both
surface and bulk (crystal structure and microstructure) phenomena are actively involved in the charge storage process. A
rational design to maximize the electrochemically active sites
for redox reactions through increasing BET surface area and
obtaining opened structures is important to further increase
the energy storage density of MnO2 powders.
A major disadvantage of packing MnO2 powders is the low
electronic conductivity to sustain high rate chargedischarge
processes. Hence, in a typical MnO2 powder electrode, an
electrically conductive enhancer, most commonly a high
surface area graphitic carbon, must be incorporated into the
powder electrode to improve its performance and a polymeric
binder for mechanical stability. The total amount of carbon
and organic binder (inactive components) ranges from 15 to
35% in weight and up to 70% of the total electrode volume,
which will undoubtedly sacrice the gravimetric and volumetric
energy densities of the MnO2 powder electrode. The
volumetric capacity is of interest for manufacturers as those
materials are studied with the aim of compact applications.
2.2
C/F g
72 to 168
(200 mA g 1)
147 (5 mV s 1)
Layered
KMnO4 or NaMnO4 in acids
at 20100 1C83
Spherical particles
KBrO3 + MnSO4 + 24 kHz
ultrasound84,85
KMnO4 + oleic acid + microwave88 Belt-like
Manganese acetate + citric acid,

80 1C89
Solution combustion Mn(NO3)2 + C2H5NO286
of techniques, including solgel dip-coating,16,33 anodic/cathodic

electrodeposition,9092 electrophoresis,9396 electrochemical
formation of manganese, and sputtering-electrochemical
oxidation.34
2.2.1 Solgel coating. Pang et al. conducted the rst
research on solgel processing of thin lm MnO2 electrodes
for EC application in 2000.16,33 Stable colloidal MnO2 was
prepared by reducing Mn(VII) (potassium permanganate)
with Mn(II) (manganous perchlorate) in an alkaline aqueous
medium,16,33 reducing tetrapropylammonium permanganate
with 2-butanol or97 adding solid fumaric acid to 0.2 M
NaMnO4,98 mixing manganese acetate with a citric acid
containing n-propyl alcohol at room temperature,99 reacting
KMnO4 with H2SO4 solutions,100,101 or reducing KMnO4 with
polyacrylamide (PAM) and polyvinyl alcohol (PVA).90
Solgel-derived nanoparticulate MnO2 thin lms were then
formed by either dip-coating or drop-coating colloidal
MnO2 directly onto conductive substrates, followed by
calcination at various temperatures.
The calcination temperature was found to have signicant
inuence on the surface morphology, specic surface area, and
specic capacitance of solgel derived MnO2 thin lms. The
highest surface areas and specic capacitances were normally
achieved by calcinating the MnO2 thin lms at temperatures
ranging from 200 to 300 1C.90 The possible reason is that
calcination at proper temperatures can generate high porosity
and a well-dened pore size distribution through evaporation
of the adsorbed water, solvent, and organic molecules, but
without further densication occurring at higher temperatures.
The specic capacitance of the solgel derived MnO2 thin lms
is also sensitive to thin lm thickness. For instance, the
ultrathin MnO2 deposits (tens to hundreds of nanometres
thick) deliver specic capacitances as high as 700 F g 1.90
The specic capacitance for thicker MnO2 lms, i.e., higher
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mass loading, is generally limited to 100200 F g 1, which

conrms that only a thin layer of MnO2, an electrochemically
active layer, is involved in the redox process.90
2.2.2 Anodic electrodeposition. Anodic electrodeposition
involves oriented diusion of charged reactive species through
an electrolyte when an electric eld is applied, and oxidation of
the charged species on the deposition surface that also serves
as an electrode. For the anodic electrodeposition of thin lm
MnO2, the electro-oxidation of Mn(II) species occurs on the
anode surfaces, shown as follows:
Mn2+ + 2H2O - MnO2 + 4H+ + 2e
(5)
Pang et al. potentiostatically prepared the rst electrodeposited thin lm MnO2 electrode for ECs in 2000.90 This
was followed by more than 30 papers dealing with anodic
electrodeposition of manganese dioxide thin lm electrodes used
in ECs.35,91,92,102143 Most of these studies focused on varying
the deposition parameters to obtain MnO2 thin lms with a wide
range of water contents, oxidation states, and Brunauer
EmmettTeller (BET) surface areas and, in turn, to achieve
enhanced electrochemical performance, e.g., high capacitance,
long-term cycling behavior, and fast charge/discharge rates.
Electrode materials with three-dimensional (3D), mesoporous and ordered/periodic architectures are desirable for
the penetration of electrolyte and reactants into the entire
electrode matrix. Among the eorts, therefore, morphologycontrolled growth has attracted much interest to obtain
more accessible electroactive sites and shorter cation
diusion lengths in MnO2 electrodes. Morphology-controlled
growth is generally achieved through controlling the
deposition parameters, lling template membranes, or using
etched, nanoporous substrates. In the rst case, the most
common surface morphology in MnO2 electrodes through
galvanostatic or potentiostatic modes is a porous, threedimensional (3D) brous network, as shown in
Fig. 8a.33,102,108,110,115,116,118,119,125,128,130132 Another type of
surface morphology through a template-free process is freestanding micro- and nano-scale bers, rods and interconnected
nanosheets prepared either by using a dilute electrolyte
(Fig. 8bd)134,135 or applying cyclic voltammetry (Fig. 8e
and f).35,108,118 In the second case, anodic Al oxide (AAO)
templates or lyotropic liquid crystalline (LLC) phases are
applied to direct the MnO2 deposition.120,129,133,136 MnO2
electrodes with oriented nanobrous, nanotubular and
mesoporous ravine-like morphologies are attained, as shown
in Fig. 9.120,129,133,136 For electrodeposition on etched, nanoporous substrates, selective dissolution of copper (Cu) from a
NiCu alloy layer is conducted to obtain a nanoporous Ni
substrate, followed by anodic electrodeposition of MnO2.138
Schematic illustrations for preparing a high-porosity Mn oxide
electrode are depicted in Fig. 10a.138 Fig. 10bd show SEM
micrographs of the as-deposited NiCu alloy lm, the nanoporous Ni lm, and the high-porosity Mn oxide electrode.138
This idea was also applied to obtain high-porosity Mn oxide
deposits based on micro-etched duplex stainless steel (DSS).139
2.2.3 Cathodic electrodeposition. Cathodic deposition of
manganese oxide thin lms can be realized through two
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Fig. 8 Typical surface morphologies for MnO2 electrodes prepared

through template-free anodic electrodeposition processes. (a) Reproduced
from ref. 106, reprinted with permission. Copyright 2003, The
Electrochemical Society; (b) reproduced from ref. 134, reprinted with
permission. Copyright 2010, Elsevier Ltd.; (c) and (d) reproduced from
ref. 135, reprinted with permission. Copyright 2010, Elsevier Ltd.;
(e) reproduced from ref. 118, reprinted with permission. Copyright
2007, Elsevier Ltd.; (f) reproduced from ref. 35, reprinted with
permission. Copyright 2005, American Institute of Physics.
Fig. 9 MnO2 nanostructures prepared by template-assisted

anodic electrodeposition. (a) Reproduced from ref. 133, reprinted
with permission. Copyright 2009, The Royal Society of Chemistry;
(b) reproduced from ref. 120, reprinted with permission. Copyright
2006, Elsevier Ltd.; (c) reproduced from ref. 136, reprinted with
permission. Copyright 2010, Elsevier Ltd.; (d) reproduced from
ref. 129, reprinted with permission. Copyright 2008, Elsevier Ltd.
electrochemical processes, depending on the reactions taking

place at the cathode surfaces. One method is electrogeneration of the base, including reactions that consume H+ ions
Chem. Soc. Rev., 2011, 40, 16971721
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Fig. 10 (a) Schematic for preparing a high-porosity Mn oxide

electrode based on micro-etched conductive substrates, (b)(d) SEM
micrographs of the as-deposited NiCu alloy lm, nanoporous Ni
lm, and high-porosity Mn oxide electrode. (Reproduced from
ref. 138, reprinted with permission. Copyright 2008, Elsevier Ltd.)
or electrolysis of water. These reduction reactions cause an

increase in the pH of the electrolyte adjacent to the cathode,
either by the consumption of H+ ions or the generation of
OH ions, which compete with the metal ion reduction reaction and become the overriding reactions. As a result, metal
deposition does not take place; instead the metal ion deposits
in the form of a hydroxide on the cathode as:
Mn2+ + 2(OH) = Mn(OH)2k
(6)
Subsequent thermal annealing will convert the manganese

hydroxide into stable manganese oxides by a dehydration
process. Zhitomirsky et al. fabricated very smooth and amorphous
MnOx lms for electrochemical supercapacitors from polyethylenimine (PEI) or chitosanMnCl2 solutions, as shown in
Fig. 11a.91,92 A similar cathodic process based on manganese
acetate-containing solutions was developed to prepare Mn3O4
lms with a porous/nanoake hierarchical architecture
(Fig. 11b).140
The other cathodic process involves electro-reduction of
Mn(VII) species occurring on the cathode surfaces as
MnO4 + 2H2O + 3e - MnO2 + 4OH
(7)
This reaction was employed for the fabrication of nanostructured manganese dioxide lms by galvanostatic, pulse,
and reverse pulse electrodeposition.141145 The deposition rate,
composition, and microstructure of the deposits are dependent
on the concentration of active MnO4 species. Electrodeposition
from a relatively dilute solution containing 0.02 M NaMnO4
resulted in the formation of brous lms with a birnessitetype crystal structure, while smoother and amorphous
lms were obtained using 0.1 M NaMnO4 solutions.141145
Typical surface morphologies of electrodeposited MnO2
lms prepared under dierent conditions are compared in
Fig. 11c and d.143
1706
Chem. Soc. Rev., 2011, 40, 16971721
Fig. 11 Cathodic deposition of manganese oxide thin lms based on

dierent cathodic reactions. (a) and (b) Electrogeneration of base;
(c) and (d) electro-reduction of Mn(VII) species. (a, reproduced from
ref. 91, reprinted with permission. Copyright 2006, Elsevier Ltd.; b,
adapted from ref. 140, reprinted with permission. Copyright 2009, The
Electrochemical Society; c and d, reproduced from ref. 143, reprinted
with permission. Copyright 2008, Institute of Materials, Minerals and
Mining.)
2.2.4 Electrochemical oxidation of Mn lms. Broughton

et al. developed a new procedure making use of physical vapor
deposition (PVD) with a glancing vapor incidence angle
(GLAD) in order to produce a chevron-type porous Mn
metallic structure, which was then electrochemically oxidized
to produce a manganese oxide electrode for ECs.34,146150 The
primary concept of thin-lm structural control using GLAD
deposition relies on self-shadowed columnar growth that is
manipulated by angular and rotational control of the substrate
with respect to the evaporation source during the deposition.34
Metallic manganese lms were deposited using the GLAD
deposition apparatus, as shown schematically in Fig. 12a.34
Fig. 12b and c show the typical as-deposited chevron-type Mn
metallic lm (Fig. 12b)147 and electrochemically oxidized
petal-shaped MnO2 (Fig. 12c).149 The porous chevron-type
structure has been converted into thin sheet-like, hydrated
MnO2. In addition to the electrochemical oxidation process,
the chevron-type Mn metallic lms were also thermally
oxidized in air to obtain manganese oxide layers. In this case,
the zig-zag architecture was replaced by a porous oxide
structure with little zigzag texture remaining, as shown in
Fig. 12d.147 The specic capacitance obtained from the
electrochemically oxidized manganese lms was generally
higher than that from thermally oxidized samples, which
further conrms that the electrochemically active sites in
manganese oxide are closely related to a hydrated and porous
structure.148
In addition to the GLAD deposition process, an electrochemical deposition process was also developed to deposit metallic
manganese lms from a BMPNTf2 ionic liquid.151153 The
electrodeposited Mn lms (Fig. 13a) were anodized in Na2SO4
aqueous solution by various electrochemical methods such
as potentiostatic, galvanostatic, and cyclic voltammetry (CV),
and transformed to Mn oxides with dierent physical characteristics, as shown in Fig. 13bd.151 The Mn oxide anodized
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Fig. 14 Highly porous thin lms containing nanobers (a) and

equiaxed particles (b) prepared through manipulating the formation parameters of charged MnO2 suspensions. (a, reproduced from
ref. 95, reprinted with permission. Copyright 2008, Elsevier Ltd.;
b, reproduced from ref. 96, reprinted with permission. Copyright
2009, Elsevier Ltd.)
Fig. 12 (a) Schematic illustration of evaporation source and substrate
geometry during GLAD deposition of Mn lms; (b) as-deposited
chevron-type Mn metallic lms; (c) chevron-type Mn metallic lms
after full electrochemical oxidation; (d) chevron-type Mn metallic lms
after full thermal oxidation. (a, adapted from ref. 34, reprinted with
permission. Copyright 2002, The Electrochemical Society; b and d,
reproduced from ref. 147, reprinted with permission. Copyright 2003,
Kluwer Academic Publishers; c, adapted from ref. 149, reprinted with
permission. Copyright 2006, The Electrochemical Society.)
reduction of KMnO4 aqueous solutions with various reducing

agents. Electrophoretic deposits are subsequently obtained
under potentiostatic or galvanostatic conditions.9396 The
deposition variables can be voltage or current density, solution
concentration, pH value, and solution temperature, but the
physicochemical features of EPD MnO2 lms are primarily
dictated by the formation process of charged MnO2 suspensions. Highly porous thin lms containing nanobers and
equiaxed particles are prepared through manipulation of the
formation parameters of charged MnO2 suspensions, as
shown in Fig. 14.95,96 Comparable electrochemical properties
(specic capacitance and cycle life) are obtained from the EPD
MnO2 lms.
2.2.6 Summary on the development of thin lm MnO2
electrodes
Fig. 13 SEM micrographs of (a) as-deposited Mn, (b) Mn oxide

potentiostatic electrode, (c) Mn oxidegalvanostatic electrode, and
(d) Mn oxidecyclic voltammetry electrode. (Reproduced from
under the CV condition had the largest surface area, highest

hydrous state, and lowest Mn valence state and showed the
highest specic capacitance.
2.2.5 Electrophoretic deposition. Another electro-assisted
coating technique is electrophoretic deposition (EPD). EPD is
achieved through the motion of charged particles in suspensions towards an electrode and deposition under an external
electric eld. Bath compositions for EPD include various
additives, which provide stabilization and charging of inorganic
particles in the suspensions. The electrophoretic deposition of
MnO2 lms involves a two-step process: rstly, a stable
suspension of charged MnO2 particles is prepared by the
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The fundamentals and technique approaches in synthesizing

thin lm or MnO2 coating electrodes have been summarized in
this chapter. Four groups of coating synthesis methods,
including solgel, electrochemical deposition, electrochemical
oxidation of metallic Mn lms, and electrophoretic deposition,
have been reviewed and discussed in detail. Solgel techniques
involve either dip-coating or drop-coating colloidal MnO2
directly onto conductive substrates, followed by calcination
at various temperatures. Calcination at elevated temperatures,
however, limits the types of substrate materials and the scope
of phase structures in which MnO2 nanostructures can be
deposited. By contrast, electrochemical deposition and electrophoretic deposition are two room temperature techniques,
opening up the prospect of deposition on various inexpensive
substrates including plastic substrates. Electrophoretic deposition is achieved through the motion of charged particles in
suspensions and deposition on the electrode surfaces. In this
case, the MnO2 particles are prepared before electrophoretic
deposition, so this technique itself cannot change the physicochemical characteristics of the MnO2 phase. The electrochemical deposition technique has some distinct advantages
for growing nanostructured electrode materials. It is generally
applicable to obtain metallic-, oxide-, and polymer-based
nanostructured materials. The composition, defect chemistry,
and even crystal structure can be manipulated through adjusting
solution concentration, solution pH value, and applied overpotential or current density.
Chem. Soc. Rev., 2011, 40, 16971721
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3. MnO2-based composite electrodes with other

elements and conducting polymers
Poor electrical conductivity (B105 O cm) has been reported
for micrometre-thick birnessite-type MnO2.55 The specic
capacitance and power characteristics of MnO2 electrodes
are ultimately limited by the high charge-transfer resistance.
It is well established that the transition metal oxides are
semiconducting in nature. Incorporation of other metal elements
into MnO2 compounds is a potential route to enhance the
electrical conductivity and charge-storage capability of
manganese oxides by introducing more defects and charge
carriers. The other consideration for alleviating the poor
electronic conductivity of MnO2 electrodes is to tailor the
electrode architecture, i.e., applying an ultrathin layer of MnO2
on the surface of a porous, high surface area and electronically
conducting structure to shorten the electron transport distance.
This can produce good electrochemical performance without
sacricing the mass-loading of the MnO2 phase. The porous
architectures can be carbon nanofoams, templated mesoporous
carbon, and nanotube assemblies.
In addition to their poor electrical conductivity, another
important issue is the electrochemical cyclability of MnO2
electrodes. Active material dissolution during electrochemical
cycling has been well recognized in some investigations,16,33,130,131
which accounts for the major capacitance loss of the MnO2
electrodes. A direct route to protect active MnO2 material
from electrochemical dissolution is to apply a coating on the
MnO2 nanoarchitecture as an eective barrier to Mn cation
permeation while allowing the electrolyte to be accessible.
Mechanical issues, such as low structural stability and exibility,
also exist in MnO2 electrodes resulting in degraded long-term
electrochemical cycle life. Hsieh et al. reported that capacitance fading can be attributed to gradual mechanical failure of
the electrode materials caused by cyclic volumetric variations
of the oxide particles upon cycling.154 To enhance the mechanical stability and exibility, many eorts have also been
attempted to incorporate conductive polymers (polyaniline,
polypyrrole, and polythiophene) and their derivatives to get
mixed MnO2polymer composite electrodes with desirable
morphologies.5659 The excellent electronic conductivity, high
stability and mechanical exibility of applied conductive polymers
enable improved electrochemical and mechanical properties of
MnO2polymer composite electrodes for ECs.5659
3.1
MnO2MeOx composite electrodes
3.1.1 MnNi mixed oxide compounds. Nickel oxides made

by the solgel method or electrochemical oxidation have been
evaluated as active materials for ECs, but they normally
exhibit low specic capacitances of 5064 F g 1.155,156 MnNi
mixed oxide electrodes for EC application were rst synthesized
through reduction of KMnO4 with Ni(II) acetatemanganese
acetate reducing solutions.44 Another chemical route, based
on thermal decomposition of the precursor obtained by
chemical co-precipitation of Mn and Ni transition metal salts,
was also developed to prepare MnNi and MnNiCo oxide
composites.157,158 By introducing 20% NiO into MnO2, the
specic capacitance increased from 166 F g 1 for MnO2 to
210 F g 1 for the Mn/Ni mixed oxide. A higher rate capacity
1708
Chem. Soc. Rev., 2011, 40, 16971721
Fig. 15 (a) Linear sweep voltammograms measured at 2 mV s 1

in (1) 0.01 M MnCl2 and (2) 0.1 M NiCl2; SEM micrographs of
(b) a-MnOxnH2O and (c) a-(Mn,Ni)xOynH2O. (Adapted from
was also observed for the Mn/Ni mixed oxides, and the
enhanced properties were attributed to the increased surface
area of the mixed oxide due to the formation of micropores.44
Electrochemical co-deposition of Mn/Ni mixed oxides from
Mn(II) and Ni(II) containing solutions was also applied to
prepare thin lm electrodes. The rate of anodic deposition for
manganese oxide is much larger than that for Ni oxide under
potentiostatic conditions, as shown in the linear sweep
voltammograms in Fig. 15a.38 The Ni content of binary
MnNi oxide electrodes is raised by applying a relatively
positive potential and a high Ni2+/Mn2+ ratio (e.g., 10 : 1)
during co-deposition. Addition of Ni oxide into the MnO2
electrodes changed the shape of the grains from spherical into
at, as shown in Fig. 15b and c, but a similar brous feature
was maintained at higher magnication.38 The a-(Mn,Ni)xOy
with B18 wt% Ni showed higher capacity, better electrochemical reversibility, and high-power characteristics in a
mixed electrolyte consisting of Na2SO4 and NaOH with
pH of 10.1.38
Potentiodynamic methods are another eective electrochemical strategy to realize co-deposition of nanostructured
and microporous nickelmanganese oxides onto inexpensive
stainless steel substrates.39 A scan rate of 200 mV s 1 between
the potential limits of 0.0 and 1.4 V was employed for the
deposition. At high scan rates, the deposition rate is low, and
accordingly, more than 300 cycles were required to deposit the
required amount of manganesenickel oxides with an atomic
ratio of 65 : 35. Enhanced electrochemical properties were
observed in this type of mixed oxide electrode. For instance,
specic capacitance (SC) values of 621 F g 1 and 377 F g 1
were obtained for CV scan rates of 10 and 200 mV s 1,
respectively.39 These values of electrochemical performance
are much higher than those obtained with just MnO2. Since
the mass loading of the manganesenickel oxides was not
reported, it is dicult to compare with other systems.
3.1.2 MnCo mixed oxide compounds. Cobalt oxides are
another candidate material for electrochemical supercapacitor
applications.8,159161 However, it is noted that cobalt oxides
have a narrower operation potential window of approximately
0.5 V and require a basic working electrolyte for supercapacitor
applications, compared with manganese oxide-based electrode
materials. Incorporation of Co oxides in Mn oxides has been
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attempted to further improve their pseudocapacitive performance.

Prasad and Miura deposited nanostructured and microporous
cobaltmanganese oxide (CMO) onto inexpensive stainless
steel substrates by potentiodynamic methods, and found that
addition of Co oxide has a benecial impact on improving
specic capacitances of MnO2.39 Similar improvement in
electrochemical properties of CoMn oxides was observed in
another study.162 However, neither the corresponding
physicochemical features were characterized nor was the
electrochemical mechanism addressed.
Some other studies using potentiostatic deposition of mixed
MnCo oxides exhibited dierent tendencies. For instance,
Chuang and Hu investigated the eects of solution pH values
on the surface morphology and chemistry of as-deposited
mixed MnCo oxides.163 Adjusting the pH of the plating
solution varied the surface morphology and Co/Mn content
ratio in the deposited oxides, but the specic capacitance
of these oxides essentially remained unchanged.163 By
contrast, Chang et al. reported that the addition of Co oxides
modied the oxide surface from a brous shape to a rather
smooth morphology (Fig. 16a and b), which may account
for the signicant reduction in the specic capacitance of the
as-deposited mixed MnCo oxide with a high Co content
(>15 wt%) (Fig. 16c).164,165 However, the addition of Co
oxides eectively inhibited the irreversible anodic dissolution
of the deposited oxide during electrochemical cycling in
aqueous KCl electrolyte (Fig. 16d).164,165 This suggests a great
improvement in electrochemical stability for mixed MnCo
oxide electrodes.
In addition to electrochemical routes, a radio-frequency
sputtering procedure was used to prepare manganesecobalt
oxide thin lms.166 Through the control of the ow rate of
Fig. 16 (a) and (b) SEM micrographs of the oxides deposited in

Mn(CH3COO)2 plating solutions with 0 and 0.2 M Co(CH3COO)
additions; (c) cyclic voltammograms of the various oxide electrodes
measured in 2 M KCl electrolyte at a potential scan rate of 5 mV s 1;
(d) variations in the specic capacitance vs. the CV cycle number for
various oxide electrodes. Curves ae present the oxides deposited with
0, 0.05, 0.1, 0.15, and 0.2 M Co(CH3COO)2 additions, respectively.
(Adapted from ref. 164, reprinted with permission. Copyright 2008,
Elsevier Ltd.)
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Fig. 17 SEM micrograph of the MnCo oxide electrode prepared by

radio-frequency sputtering. (Adapted from ref. 166, reprinted with
permission. Copyright 2010, The Electrochemical Society.)
oxygen, sputtering pressure, sputtering power, and annealing

temperature, mixed oxide layers with petal-shaped morphology were obtained, as shown in Fig. 17.166 A maximum
specic capacitance of 256 F g 1 was retained at the 2000th
cycle of potential cycling, demonstrating long-term operational
stability and good specic capacitance at a high sweep rate of
100 mV s 1.166
3.1.3 MnFe mixed oxide compounds. Iron possesses
various valence states making it a promising electrode material
for supercapacitors. MnFe2O4, a MnFe mixed oxide material,
was recently found to exhibit pseudocapacitance in aqueous
NaCl solutions. MnFe2O4 was synthesized via a precipitation
technique in basic aqueous solutions with a MnSO4 to FeCl3
ratio of 2 : 1, followed by a subsequent calcination process at
dierent temperatures for 2 h in a N2 atmosphere.167 It was
found that large capacitances are associated with the Mn2+
ions in the tetrahedral sites in the spinel structure. Pseudocapacitance was observed only for crystalline, rather than
amorphous MnFe2O4 treated at temperatures o 200 1C, as
shown in the cyclic voltammograms (Fig. 18) taken from MnFe
mixed oxide electrodes annealed at dierent temperatures.167
This tendency is essentially dierent from what was observed
for MnO2 electrodes, but a clear understanding has not been
reached yet.
Another technique to incorporate iron oxides into manganese oxide electrodes is electrochemical co-deposition.168170
MnFe oxides were prepared on graphite substrates by anodic
deposition from 0.25 M Mn acetate aqueous solutions with
various amounts of FeCl3 up to 0.15 M.168170 Experimental
results indicated that the incorporated iron was present as
di- and tri-valent oxides. In situ X-ray absorption spectroscopy
(XAS) results (Fig. 19) conrm that the pseudocapacitive
behavior of the MnFe oxides is associated with the reversible
variations in the oxidation states of both the Mn and Fe
cations during electrochemical cycling.170 It has been found
that through introduction of Fe oxide, the degree of change in
the Mn oxidation state increases from 0.70 to 0.81 within the
potential range of 01 V. The specic capacitance of Mn90Fe10
oxide (255 F g 1) is higher than that of the pure Mn oxide
(205 F g 1). This experimental evidence suggests that Fe
addition enhances the electrochemical performance through
improving the electrical conductivity of manganese oxides.170
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Fig. 18 CV curves of coprecipitated electrodes consisting of MnFe2O4/carbon black powders treated at dierent temperatures: (a) 50 1C and
200 1C, (b) 300 1C, 350 1C, 400 1C and 500 1C. Scan rate was 20 mV s 1. (Adapted from ref. 167, reprinted with permission. Copyright 2005,
The Electrochemical Society.)
Fig. 19 (a) Twenty-one serial in situ MnK edge XAS spectra for Mn90Fe10 oxide measured at various applied potentials. (b) The dependence of
the Mn oxidation state with respect to the applied potential, obtained from (a). (Adapted from ref. 170, reprinted with permission. Copyright 2008,
Elsevier Ltd.)
A two-step spray pyrolysis-electrophoretic deposition

(SP-EPD) process was employed to prepare nanocrystalline
MnFe mixed oxide electrodes.171 The iron-containing
manganese oxide powders were synthesized from manganese
acetate and iron nitrate solutions at 400 1C. The as-processed
powders were subsequently deposited onto graphite substrates
via electrophoretic deposition. Structural analysis revealed
that the as-deposited coatings exhibited a nanocrystalline
Mn3O4 phase. The specic capacitance of the as-deposited
Mn-oxide coating was increased from 202 F g 1 to 232 F g 1
when 2 at% Fe was added.171 Moreover, enhanced electrochemical cyclability was observed for the iron-added coatings
(B78% of the initial maximum capacitance) compared with a
pure MnO2 electrode (B60% of its maximum value).171
3.1.4 MnX (X = Pb, V, Ru, Mo and Al) mixed oxides. In
addition to Ni, Co and Fe, other metallic elements have been
introduced with the intention to further improve the electrochemical performance of Mn oxide electrodes. Lead oxides
were added into Mn oxide electrodes through reduction of
KMnO4 with Pb(II) acetatemanganese acetate reducing
solutions.44 By introducing 20% Pb into MnO2, the specic
capacitance increased from 166 F g 1 estimated for MnO2 to
185 F g 1 for Mn/Pb mixed oxides, which was attributed to
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Chem. Soc. Rev., 2011, 40, 16971721
the increased surface area of the mixed oxide due to the

formation of micropores.44
Vanadium oxide (V2O5) was introduced into MnO2 thin
lm electrodes by electro-oxidation of Mn2+ precursors in
aqueous solution with VO3 .40,172 XRD analysis conrmed
that the presence of vanadate ions inhibits the growth of the
Mn oxide lattice, leading to an amorphous-like phase in the
as-deposited mixed MnV oxide.40,172 The infrared spectrum
exhibited bands attributable to V2O5, suggesting that protonation and dehydration of VO3 occur to form the polymeric
structure. The electron spin resonance results suggest that
Mn3+ ions do not exist in the oxide network, but pair with
unreacted VO3 .40,172 When annealed at elevated temperatures, the formation of Mn2+ occurs only in the mixed MnV
oxide lms. This implies that electron transfer from thermally
generated V4+ cations to neighboring Mn cations occurs.40,172
Enhanced voltammetric response of the heat treated Mn/V
oxide lm was observed in a borate solution, compared with
that of pure manganese oxide, which can be attributed to the
higher electrical conductivity of the mixed MnV oxide
lms.40,172
Rutheniummanganese oxide (RunMn1 nOx) has been
prepared by oxidative co-precipitation through mixing of Mn(VII)
(potassium permanganate), Mn(II) (manganese acetate), and
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Ru(III) (ruthenium chloride) in a neutral aqueous solution at

room temperature.42 The proposed formation reactions are as
follows:42
2MnO4 + 3Mn2+ + 2H2O - 5MnO2 + 4H+
Ru3+ + 3H2O - Ru(OH)3 + 3H+
4Ru(OH)3 + O2 - 4RuO2 + 6H2O
(8)
(9)
(10)
At an appropriate calcination temperature (e.g., 170 1C), the

mixed RuMn oxide powders are in a hydrous amorphous
state with improved electrochemical properties (higher specic
capacitance and lower charge transfer resistance, as shown in
the CV curves in Fig. 20a and impedance spectra in Fig. 20b),
when compared with pure Mn oxide.42 The reduced charge
transfer resistance and enhanced voltammetric response observed
in the mixed RuMn oxide powders can be attributed to a
higher electronic conductivity induced by the Ru-doping.
In addition to chemical co-precipitation, a co-electrospinning
technique was employed to synthesize MnOxRuO2 composite
ber mats through two isolated spinnerets.173 During the
electrospinning process, two types of precursor solutions,
based on Mn acetylacetonate + PVAc and RuCl3 + PVAc,
were transferred simultaneously into separate syringes
mounted on the electrospinning apparatus, as schematically
shown in Fig. 21a.173 The as-electrospun and calcinated
MnOxRuO2 ber mats at dierent temperatures are shown
in Fig. 21bd. The electrochemical performance using the
co-electrospun MnOxRuO2 ber mats calcined at 300 1C
exhibited a high specic capacitance of 208.7 F g 1 at a scan
rate of 10 mV s 1.173 The co-electrospinning technique shows
high versatility to preparing composite electrodes with both
high surface activity and high conductivity for EC applications.
MnMo mixed oxide thin lms were deposited anodically
on a platinum substrate by cycling the electrode potential
between 0 and +1.0 V vs. Ag/AgCl in aqueous Mn(II) solutions
containing molybdate anions (MoO42 ).43 In this process,
only Mn(II) cations were electro-oxidized to form MnO2.
The MoO42 ions were incorporated into MnO2 by protonation and dehydration,43 which is similar to the formation
of MnO2V2O5 mixed oxides mentioned above.40,172 Cyclic
voltammetry of the Mn/Mo oxide electrode in an aqueous
0.5 M Na2SO4 solution exhibited pseudocapacitive behavior
Fig. 21 (a) Schematic diagram of the co-electrospinning process used

to synthesize MnOxRuO2 ber mats. (b) SEM image of as-spun
MnOxRuO2/PVAc composite ber mats prepared by electrospinning.
(c) SEM image of MnOxRuO2 ber mats calcined at 300 1C. (d) SEM
image of MnOxRuO2 ber mats calcined at 400 1C. (Adapted from
with a higher capacitance and better rate capability than that

for pure Mn oxide, most likely due to an increase in electrical
conductivity of the mixed oxide lm.43
Aluminium (Al) is another element that has been added into
manganese oxide electrodes.45,174 Al-doped MnO2 compounds
were synthesized either by an electrochemicalhydrothermal
route45,174 or through a high energy ball-milling technique.45,174
The electrochemicalhydrothermal technique can be regarded
as anodic electrodeposition in an autoclave at solution temperatures ranging from 80 1C and 140 1C.45,174 The Al-substituted,
g-MnO2 materials exhibited a higher specic capacitance than
non-substituted MnO2, consistent with the benecial eect of
substitution on the surface area.45,174 For high energy ballmilling, a mixture of pure aluminium and manganese dioxide
powder with a desired atomic ratio was put into a stainless
steel vessel with steel balls at a ball-to-powder weight ratio of
20 : 1. The high energy ball-milling was conducted at 250 rpm
for 50 h. The Al(0.05)/Mn(0.95)O2 electrode showed the largest
Fig. 20 (a) Cyclic voltammograms and (b) Nyquist plots for RunMn1 nOx (n = 0.1) and MnO2 electrodes at dierent applied potentials in the
frequency range of 10 2104 Hz. Both powders were calcined at 170 1C. (Adapted from ref. 42, reprinted with permission. Copyright 2009, Elsevier
Ltd.)
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specic capacitance among the MnO2 samples with various Al

contents.45,174 Excellent electronic conductivity for Al doped
MnO2 was considered to be responsible for the enhanced
electrochemical performance of doped MnO2.45,174
3.1.5 Summary of incorporation of other metal elements in
MnO2. A core challenge in EC design is the identication
of suitable electro-active materials. The poor electrical conductivity of MnO2 limits the specic capacitance and power
characteristics of MnO2 electrodes through high chargetransfer resistance. Metal elements, including Ni, Fe, Co,
V, Mo, Al, Pb, and Ru, can be incorporated into MnO2
compounds to enhance the electrical conductivity and
charge-storage capability by introducing more defects and
charge carriers. Enhancement of specic capacitance was
observed for Ni-, Fe-, V-, Mo-, Al-, Pb-, and Ru-containing
MnO2 electrodes, and was mainly attributed to the improved
electrical conductivity of the composite electrodes. The
amount of metal additives has signicant eects on the
electrochemical properties. For instance, for MnFe mixed
oxides, the specic capacitance increases with addition of Fe
oxides and reaches a maximum value at a Mn : Fe ratio of
9 : 1. A further increase in the amount of Fe oxide may cause a
reduction in the specic capacitance.170 However, contradictory
results have been reported for the eect of Co oxide additions
on the specic capacitance of MnO2 electrodes. Some research
work exhibited benecial eects by introducing Co oxides,
whereas other studies showed an opposite tendency.39,162 It is
interesting to note that the addition of Co oxides may signicantly suppress the irreversible dissolution of the deposited
oxide during electrochemical cycling in aqueous KCl electrolyte, resulting in a great improvement in the electrochemical
stability of mixed MnCo oxide electrodes. Thus far, however,
an unambiguous understanding on the eect of introducing
metal elements to form mixed oxide electrodes on the subsequent electrochemical properties is lacking, which is critical
to optimizing manganese oxide-based electrodes for EC
application.
Note that similar chemical modication routes have been
extensively applied to improve the electrochemical properties
of MnO2-based batteries such as Li/MnO2. Layered LiMnO2
and spinel LiMn2O4 are the most attractive positive electrode
materials for the Li/MnO2 batteries. Layered LiMnO2 has
high theoretical capacity but poor capacity retention induced
by structural instability (phase transition from the layered
structure to spinel).175,176 Partial substitution of Mn with Co
or Ni has been employed to improve the electrochemical
reversibility of layered LiMnO2 electrodes.175,177179 For the
stable spinel LiMn2O4, on long term cycling, slight capacity
fading was also observed in the Li/MnO2 batteries, which was
attributed to slow dissolution of the LiMn2O4 electrode in
the electrolyte and the onset of the JahnTeller distortion
for a deeply discharged LiMn2O4 electrode.180182 There are
various strategies to alleviate or eliminate the dissolution
and JahnTeller distortion issues, including the substitution
of JahnTeller ion Mn3+ by some other trivalent cations
(such as Al3+, Fe3+, Ni3+, Co3+, or Cr3+)183187 and surface
modication of the LiMn2O4 electrode with some oxide
coatings (such as ZrO2 or AlPO4).188,189 Generally, chemical
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Chem. Soc. Rev., 2011, 40, 16971721
modication in Li/MnO2 batteries aims to address primarily

the structural instability of electrode materials during deep
insertion/extraction of Li, which is distinct from MnO2
ECs since fast surface or near-surface redox reactions are
predominant in ECs. However, the chemical modication
strategies for Li/MnO2 batteries may shed light on further
improvement of electrochemical cyclability in MnO2 ECs.
3.2 MnO2polymer composite electrodes
3.2.1 MnO2poly(o-phenylenediamine) (PPD). During
electrochemical cycling, manganese oxide electrodes undergo
a reductive-dissolution process when exposed to even mildly
acidic and near-neutral electrolytes, generating soluble Mn(II)
species.190192
MnO2 + H+ + e - MnOOH
(11)
MnOOH + 3H+ + e - Mn + 2H2O
(12)
Therefore, MnO2 is limited to neutral or basic aqueous

electrolytes, and the specic capacitance and rate capacity of
MnO2 electrodes are diminished by employing less-desirable
insertion cations such as Li+, Na+, and K+, compared with
the fast H+ insertion process. To overcome the limitation
associated with MnO2, a self-limiting electropolymerization
strategy has been developed to apply ultrathin, conformal
poly(o-phenylenediamine) (PPD) coatings onto nanostructured
MnO2 ambigel electrodes.54,55 Self-limited PPD lms, electrodeposited from an aqueous borate buer solution with
pH = 9 on planar indium-tin oxide (ITO) electrodes, have a
thickness of less than 10 nm. These hybrid PPDMnO2
nanoarchitectures are stable in aqueous acid electrolytes upon
electrochemical cycling. The ultrathin PPD coating serves as
an eective barrier to the electrolyte, protecting the underlying
MnO2 nanoarchitecture from electrochemical dissolution.54,55
However, based on conductive-probe atomic force microscopy (CP-AFM) results, the hybrid PPDMnO2 electrode
structures were found to exhibit degraded electronic conductivity, compared with native MnO2 ambigel lms supported
on indium tin oxide (ITO) substrates.54,55 Fig. 22 shows the
topography and current images for uncoated and PPDcoated
MnO2 ambigel lms supported on ITO.55 Following the selflimiting electrodeposition of the PPD coating onto the MnO2
ambigel, a 20-fold reduction in conductivity was observed in
the hybrid structures. These results demonstrate the feasibility
of constructing hybrid congurations with metal oxides and
polymers for ECs; however, a polymer coating based on
poly(o-phenylenediamine) is not an optimal choice due to its
poor electrical conductivity.
3.2.2 MnO2polyaniline (PANI). PANI is one of the most
promising electronically conducting polymers with potential
applications as ECs because of its easy synthesis, high stability,
and good conductivity. The addition of PANI can be either
chemical or electrochemical. The rst MnO2PANI composite
electrode was prepared through a two-step electrochemical
route: nanostructured MnO2 was potentiodynamically deposited
on a polyaniline (PANI) matrix synthesized through an
electrochemical method.56 Fig. 23a and b show the morphology of the as-deposited PANI matrix and the MnO2PANI
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Fig. 22 Simultaneously acquired topography and current images of

uncoated and PPD-coated MnO2 ambigel lms supported on ITO.
(a) and (b) topography and current images of an uncoated sample;
(c) and (d) topography and current images of a PPD-coated sample.
Below each image is the corresponding plot along the white lines
across the AFM images. (Reproduced from ref. 55, reprinted with
permission, copyright 2006, American Chemical Society.)
composite.56 Optimization of thickness of the PANI lm and

the amount of MnO2 deposition leads to a specic capacitance
of 715 F g 1 and an energy density of about 200 Wh kg 1 at a

chargedischarge current density of 5 mA cm 2, as shown in
Fig. 23c.56 By contrast, in another study, a PANI coating was
electrochemically polymerized on MnO2 nanoparticles.193 To
enhance the interaction of MnO2 and PANI, the MnO2
nanoparticles were modied by triethoxysilylmethyl N-substituted
aniline (ND42) before the PANI electro-polymerization.
Signicant enhancement of specic capacitance in the
PANINDMnO2 lm was observed, compared with the
PANIMnO2 lm prepared in a similar manner, indicating
that the presence of the coupling reagent can improve the
electrochemical performance of PANIMnO2 composite
lms.193
In addition to the two-step electrochemical method, electrochemical co-deposition was applied to prepare MnO2PANI
composite electrodes.194 Electro-codeposition was conducted
on carbon cloth from solutions of aniline and MnSO4 through
potential cycling between 0.2 and 1.45 V (vs. SCE). The
codeposition of PANI with MnO2 produced larger eective
areas for hybrid lms with brous structures. The lms
obtained displayed pseudocapacitive behavior from 0 to
0.65 V vs. SCE in an acidic aqueous solution (1.0 M NaNO3
at pH = 1). A specic capacitance of 532 F g 1 at 2.4 mA cm 2
discharging current and a coulombic eciency of 97.5% over
1200 cycles with 76% capacitance retention were achieved.194
Chemical polymerization is another common route to
incorporate PANI into MnO2 electrodes. A MnO2PANI
composite was prepared through oxidizing an aniline thin lm
with a KMnO4 solution on a porous carbon electrode.195 At a
rate of 50 mV s 1, the carbon/MnO2PANI composite electrode
and the MnO2PANI lm produced specic capacitances as
high as 250 and 500 F g 1, respectively. The specic capacitance maintained 61% of the initial specic capacitance after
Fig. 23 (a) and (b) Morphology of the as-deposited PANI matrix and MnO2PANI composite; (c) specic capacitance and specic energy of
MnO2PANI electrodes at various discharge current densities with various specic masses of MnO2. The specic mass of PANI was kept constant
at 4 mg cm 2. (Adapted from ref. 56, reprinted with permission. Copyright 2004, The Electrochemical Society.)
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Fig. 24 Schematic illustrations for the formation of PANI-intercalated

manganese oxide. (Reproduced from ref. 197, reprinted with permission.
Copyright 2007, Elsevier Ltd.)
5000 cycles mainly due to slow dissolution of MnO2 in the

electrolyte.195 Another similar oxidative polymerization process,
with aqueous ammonium peroxydisulfate solution as an
oxidizing agent, was developed to polymerize the aniline
monomer and to form PANI/MnO2/MWCNTs organic
inorganic hybrid nanoarchitectures.196 PANI not only served
as a physical barrier to prevent the underlying MnO2 from
reductive-dissolution processes, but also boosted the specic
energy storage as an electroactive material for energy storage
in the acidic mixed electrolytes. A higher specic capacitance
of 384 F g 1 and a much better SC retention of 79.9% over
1000 continuous charge/discharge cycles than those for the
MnO2/MWCNTs nanocomposite were achieved.196
An exchange reaction of PANI with n-octadecyltrimethylammonium(OCTA)-intercalated manganese oxide in the
N-methyl-2-pyrrolidone solvent to prepare a novel PANIintercalated layered manganese oxide (PANIMnO2) nanocomposite was developed.197 A schematic illustration for the
formation of PANI-intercalated manganese oxide nanocomposites is shown in Fig. 24.197 A maximum specic capacitance
of 330 F g 1 was obtained from the PANIMnO2 nanocomposite at a constant current density of 1 A g 1, showing
improvements of 76% and 59% compared with those of PANI
(187 F g 1) and manganese oxide (208 F g 1). The enhanced
properties are likely due to improved electronic conductivity
of the PANIMnO2 nanocomposite.197
3.2.3 MnO2polypyrrole (PPy). Sivakkumar et al.
prepared CNT/PPy/hydrous MnO2 composites by in situ
redox reaction of KMnO4 and pyrrole.58 The specic capacitance
values of the CNT/PPy/MnO2, CNT/MnO2 and PPy/MnO2
composites were estimated using CV techniques to be 281, 150
and 32 F g 1 at a scan rate of 20 mV s 1 with a mass loading of
0.64 mg cm 2 of hydrous MnO2.58 This work was followed by
a similar chemical synthesis of PPy/hydrous MnO2 on poly(4-styrenesulfonic acid) (PSS) dispersed multiwall carbon nanotubes (MWCNTs).198 The good electrochemical performance
of the ternary CNT/PPy/MnO2 composite in comparison with
the binary composites is believed to be due to the good
electrical conductivity of the CNT substrates as well as eective
dispersion of hydrous MnO2 in the composite electrode.
However, the composite with MnO2 particles embedded in a
PPy matrix showed low electrical conductivity and poor
electrochemical properties.58 By contrast, MnO2 embedded
PPy nanocomposite thin lm electrodes prepared by
electrochemical deposition show a dierent tendency.199
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Chem. Soc. Rev., 2011, 40, 16971721
The MnO2/PPy nanocomposite electrodes show signicant

improvement in the redox performance. The specic capacitance
of the nanocomposite was remarkably high (B620 F g 1)
in comparison to that of MnO2 (B225 F g 1) and PPy
(B250 F g 1).199 It is reasonable to conclude that the electrochemical properties of the MnO2/PPy composite electrodes are
sensitive to the preparation technique and procedures.
A PPy-intercalated layered MnO2 nanocomposite with
molecular-level hybrid features has been synthesized by a
delaminationreassembling process,200 which is similar to the
process described in Fig. 24.197 Based on XRD tests, the basal
spacing of MnO2 in the PPynanocomposite was determined
to be 1.38 nm.200 The room-temperature conductivity of the
PPyMnO2 nanocomposite was 0.13 S cm 1, which was
45 orders of magnitude higher than that of the pristine
manganese oxide (6.1 106 S cm 1).200 The improved specic
capacitance of the PPyMnO2 nanocomposite (290 F g 1)
compared with that of the MnO2 (221 F g 1) was attributed to
a combination of the conductivity eect and the high specic
capacitance of PPy.
3.2.4 MnO2polythiophene (PTh). Polythiophene and its
derivatives generally possess excellent electronic conductivity,
high chemical stability, and reasonable mechanical exibility,201
but they provide low electrochemical energy density. The
combination of MnO2 with its high energy storage capacity
and highly conductive and exible PThs produces MnO2PTh
composite electrodes which have high specic capacitance,
rate capacity and improved electrochemical cyclability. Rios
et al. developed one type of poly(3-methylthiophene)-modied
MnO2/Ti electrode for electrochemical supercapacitors.57 The
poly(3-methylthiophene) polymer lms were prepared on
the MnO2/Ti electrodes through galvanostatic deposition at
2 mA cm 2. The electrochemical results showed a very
signicant improvement in the specic capacitance of the
oxide due to the presence of the polymer coating.57
Another PTh derivative, poly(3,4-ethylenedioxythiophene)
(PEDOT), was also incorporated to form MnO2/PEDOT
coaxial nanowires by a co-electrodeposition method.59 The
conductive, porous, and exible PEDOT shell facilitates
electron transport and ion diusion into the MnO2 core and
protects the electrode from mechanical failure. Fig. 25ae
illustrates the relationship between the coaxial nanowire
structures and the applied potential during electrodeposition.59
The structures of the coaxial nanowires, such as PEDOT shell
thickness and nanowire length, can be controlled by varying
the applied potential. The combination of MnO2 and PEDOT
into 1D nanostructures showed excellent electrochemical and
mechanical properties for energy storage applications.59
In addition to electrochemical methods, PEDOT has been
chemically co-deposited with MnO2 to form a PEDOT/MnO2
nano-composite on poly(styrene sulfonate) (PSS) dispersed
multiwalled carbon nanotubes (MWCNTs).202 In this chemical
process, EDOT monomers and Mn2+ ions were oxidized
by KMnO4 solutions to form MWCNTsPSS supported
PEDOT/MnO2 nano-composites.202 A small amount of
PEDOT acted as a conducting link between MnO2 and the
MWCNTs, which greatly enhanced the utilization of MnO2 in
the electrode. The long-term stability and high specic
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Ternary MnO2polymerCNT composites have also been

evaluated as EC electrode materials. The enhanced electrochemical performance (high specic capacitance and long-term
stability) of ternary CNT/PPy/MnO2 composites is believed to
be due to the good electronic conductivity of the polymer
CNT substrates as well as eective dispersion of hydrous
MnO2 within the composite electrode.
3.3 MnO2nanostructured carbon composites
Fig. 25 (a) SEM image of MnO2/PEDOT coaxial nanowires (0.75 V).

(b) TEM image from a single coaxial nanowire (0.75 V). (c and d)
Elemental mapping of S and Mn from the boxed area in (b).
(e) PEDOT shell thickness variation with applied potential. (Reproduced
from ref. 59, reprinted with permission, copyright 2008, American
Chemical Society.)
capacitance of MWCNTPSS/PEDOT/MnO2 nano-composite

electrodes demonstrate that the synergistic combination of
MWCNTPSS, PEDOT, and MnO2 has advantages over just
the sum of the individual components.202
3.2.5 Summary of MnO2polymer nano-composite electrodes.
In order to improve the electrical conductivity, chemical
stability, mechanical stability, and exibility of MnO2 electrodes,
poly(o-phenylenediamine), polyaniline, polypyrrole, and
polythiophene and their derivatives have been introduced.
An ultrathin, conformal poly(o-phenylenediamine) coating
can be applied onto nanostructured MnO2 ambigel electrodes.202
The polymer coating protects the underlying MnO2 nanoarchitecture from electrochemical dissolution, demonstrating
the feasibility of using low-cost metal oxides (manganese and
iron oxides) in the high protonic conductivity media desired
for ECs.202 However, PPD-coated MnO2 ambigels suer from
a signicant reduction in electrical conductivity, making them
an unfavorable option for EC applications.202
More eorts have been dedicated to incorporate polyaniline, polypyrrole, and polythiophene conductive polymers
to generate MnO2polymer composite electrodes with desirable
morphologies. The preparation techniques can be either
chemical or electrochemical. The conductive polymers are in
the form of a conductive substrate,56 a conformal, ultra-thin
layer on MnO2 nanostructures,57,59,193,195197 or can be intercalated into layered MnO2 compounds to obtain molecularlevel hybrid features.197,200 The excellent electronic conductivity,
high stability, and mechanical exibility of the applied conductive
polymers enable improved electrochemical and mechanical
properties for MnO2polymer composite electrodes for ECs.59
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3.3.1 MnO2carbon nanotubes (CNTs). CNTs are the most

representative nanostructured carbons with one dimensional
tubular structures and exhibit outstanding physicochemical
properties such as high electrical conductivity, high mechanical strength, high chemical stability, and high activated
surface areas. The potential of CNTs as electrodes in ECs
has been exploited extensively in the last decade. However, the
specic capacitance of CNTs is generally one order magnitude
smaller than that of the transition metal oxides, which limits
their practical applications. A combination of MnO2 and
CNTs may, however, take advantage of both the excellent
electrical conductivity and chemical stability of CNTs and the
high specic capacitance of MnO2. The incorporation of
MnO2 on CNT architectures can be realized through chemical
co-precipitation, thermal decomposition, electrophoretic, and
electrochemical deposition.
Chemical co-precipitation is the most widely applied technique
to prepare MnO2CNT composite electrodes. Chemical
co-precipitation is achieved either by KMnO4 reducing
procedures,50,203207 through hydrothermal oxidation of
manganese acetate (Mn(CH3COO)2),208 or by oxidizing
MnSO4 with (NH4)2S2O8 and (NH4)2S2O4.209 CNTs are added
and well dispersed in the co-precipitation solutions. In an
aqueous KMnO4 solution, CNTs were found to act as a
reducing agent and also as substrates for the heterogeneous
nucleation of MnO2 deposits.210,211 Varying the solution
composition, pH value, solution temperature, and reaction
time signicantly alter the morphology and composition of the
MnO2CNT composite electrodes. Fig. 26a and b show how
solution composition aects the morphology and composition
of the MnO2CNT composite during co-precipitation.208
Chemical co-precipitation generally leads to MnO2CNT
composite structures with good coverage of MnO2 on CNT
substrates and desirable interconnected micro- and nanopores
(good conduction of both electrons and the charge-balancing
ions), which are critical to achieve enhanced electrochemical
properties.
Thermal decomposition is another chemical route to
form MnO2CNT composite electrodes. Carbon nanotubes
prepared by typical chemical vapor deposition (CVD) technique
were treated in a 30 wt% HNO3 to improve the wetting ability
of the CNT surface, followed by addition of a 50 wt%
Mn(NO3)2 aqueous solution and calcination at 250 1C in air
for 2 h.49 A uniform manganese oxide layer was formed on the
CNT surface (Fig. 26c and d).49 More recently, Cui et al.
reported a thermal decomposition process to prepare uniformly
dispersed manganese oxide nanoparticles within a millimetrelong carbon nanotube array (CNTA).212 Mn(CH3COO)2
4H2O/ethanol solutions were employed to introduce Mn
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Fig. 26 (a) and (b) MnO2CNT composites synthesized by chemical

co-deposition with Mn(CH3COO)24H2O/MWCNT at a ratio of 1 : 2
(a) and 3 : 1 (b) (reproduced from ref. 208, reprinted with permission,
copyright 2008, IOP Publishing Ltd.); (c) and (d) MnO2CNT composites synthesized by thermal oxidation of Mn(NO3)2 at 250 1C
in air for 2 h (reproduced from ref. 49, reprinted with permission.
Copyright 2006, Elsevier Ltd.); (e) and (f) MnO2millimetre-long
CNTA composites prepared by a thermal decomposition process using
Mn(CH3COO)24H2O/ethanol solutions as Mn cation sources.
cations adsorbed on the CNT surface. The CNTA bundle

features were maintained even after calcination at 300 1C
(Fig. 26e), and the decorated nanoparticles were well dispersed
along the CNTs (Fig. 26f).212
Deposition of MnO2 on CNTs with the assistance of an
electric eld is another feasible way to form MnO2CNTs
composite electrodes. The processes can be categorized into
electrophoretic and electrochemical deposition. Electrophoretic

co-deposition involves the oriented movement and deposition
of charged particles (MnO2 and CNTs) driven by an external
electric eld. Deposit composition and lm thickness are
controlled by varying the MnO2/CNTs ratio in aqueous
suspensions, deposition time, and voltage. This method enabled
the formation of porous nanostructured composite lms with
pore sizes of 10100 nm.213 Electrochemical deposition
involves redox reactions to form MnO2 deposits on CNTs,
which can be achieved either by co-deposition with CNTs on
current collectors53 or by nucleation and growth of MnO2 on
CNT-decorated substrates.52,214218 During electrochemical
co-deposition, the rate/nucleation mechanism of MnO2
deposition was signicantly inuenced by the introduction of
MWCNTs in the plating baths.53 The specic capacitance of
thick MnO2MWCNT composites (310 mm) gradually
decreased from 160 to 80 F g 1 with increasing MnO2 loading
of the deposits from 1.5 to 4.5 mg cm 2, which was attributable
to the relatively poor utilization of electroactive materials.53
More eorts were dedicated to incorporating nano-scale
MnO2 deposits on CNT architectures through electrochemical
deposition.52,214218 Typical cases are petal-shaped g-MnO2
deposits on CNTs (Fig. 27a)215 and manganese oxide nanoowers on vertically-aligned CNT arrays (Fig. 27b and c).214
Nanoscale MnO2 incorporated into CNTs yielded signicant
capacitance enhancement, with a MnO2-normalized capacitance up to 700 F g 1.215 However, the overall specic
capacitance was generally limited to 200 F g 1 due to the
relatively low weight loading of MnO2.
3.3.2 MnO2nanographite sheets. Nanographite materials,
obtained by exfoliation of graphite, exhibit a large surface area
and more edge sites for anchoring functional groups. The
graphite structural units aggregated in an irregular fashion
create more void spaces for electrolyte transport. This has
motivated some research eorts to use nanographite sheets as
conductive supporting materials for manganese oxide-based
ECs.219221 Nanographite sheet materials prepared through
exfoliation of graphitic oxide can have a BET surface area in
excess of 200 m2 g 1, and the number of graphene sheets is
within the range of a several tens of sheets. A representative
SEM micrograph of nanographite sheets is illustrated in
Fig. 28a.221 A chemical co-precipitation process, based
on reduction of KMnO4 or oxidation of MnSO4,219221
was applied to prepare the MnO2nanographite composite
Fig. 27 Nano-scale MnO2 deposits formed on CNT architectures through electrochemical deposition. (a) Surface morphology of petal-shaped
g-MnO2 deposited on CNTs; (b) and (c) manganese oxide nanoowers on vertically-aligned CNT arrays. (a, reproduced from ref. 215, reprinted
with permission. Copyright 2008, Elsevier Ltd.; b and c, reproduced from ref. 214, reprinted with permission. Copyright 2008, American Chemical
Society.)
1716
Chem. Soc. Rev., 2011, 40, 16971721
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Fig. 28 (a) A representative SEM micrograph of nanographite

sheets; (b) MnO2nanographite composite electrode prepared by
chemical co-precipitation process, based on reduction of KMnO4 or
oxidation of MnSO4. (Reproduced from ref. 221, reprinted with
permission. Copyright 2008, Elsevier Ltd.)
electrodes (Fig. 28b). Although pure nanographite sheets

showed a very low capacity of less than 10 F g1, the capacity
per net amount of MnO2 increased linearly with the nanographite content. This implies that the utilization ratio of MnO2
increased with nanographite content, mainly due to the larger
contact area between MnO2 and the electrolyte and the higher
conductivity achieved in the composite electrodes.219221 It is
worthy, however, to note that the specic capacitance
calculated by per amount of composite materials in the
electrode levels o with a continuous increase in the nanographite content. The overall specic capacitances of MnO2
nanographite composite electrodes were found to range from
120 to 160 F g 1.219221
3.3.3 MnO2carbon nanofoams/aerogels. Carbon nanofoams, also recognized as carbon aerogels, are particularly
attractive nanoarchitectures for EC applications due to their
intrinsic physical characteristics that include high specic
surface areas (up to 1000 m2 g 1), interconnected mesopores
or macropores with pore sizes ranging from nanometres to
micrometres, durable monolithic shape, and high electronic
conductivity (10100 S cm 1).47,65,222228 The physical characteristics of carbon nanofoams enable the mass loadings of
incorporated MnO2 to be maximized to optimize the desirable
structural and electronic characteristics of the carbon nanofoams and MnO2.
A microemulsion-templated solgel polymerization method
is a common route to prepare carbon aerogels, based on
pyrolysis of a resorcinol-formaldehyde (RF) gel.47,65,222228
In this case, all reactants including formaldehyde, resorcinol,
and deionized water are mixed, cured, dried, and pyrolyzed to
obtain the conductive carbon nanofoams.47,65,222228 A reducing
process of aqueous permanganate with carbon nanofoams and
direct electrodeposition were developed to incorporate homogeneous MnO2 deposits within the carbon nanofoam electrodes
(Fig. 29a).227 The distribution of the MnO2 coating is vital to
increase the electrochemical capacitance of the carbon nanofoam electrode without a penalty of charge transfer resistance
increase. For instance, an acid-deposited MnO2carbon
electrode indicated a much higher charge-transfer resistance
(Nyquist plots in Fig. 29b), compared with the bare carbon
nanoform and the neutral-deposited MnO2carbon electrode,
which was attributed to the poor electrical conductivity of the
4 mm thick MnO2 crust.47 Therefore, variation in the carbon
nanofoam pore structure, such as larger pore sizes and higher
This journal is
Fig. 29 (a) Representative TEM micrograph showing homogeneous

MnO2 deposits within carbon nanofoam electrodes; (b) Nyquist plots
for MnO2carbon nanofoam electrodes prepared under dierent
conditions. (a, reproduced from ref. 227, reprinted with permission.
Copyright 2009, American Chemical Society; b, reproduced from
ref. 47, reprinted with permission. Copyright 2007, American Chemical
Society.)
overall porosity, could lead to higher mass loadings of MnO2

and better utilization of internal pore volume. In addition,
tuning the structural features of the nanoscale MnO2 deposits
may improve the achievable specic capacitance for the
composite electrodes.47
3.3.4 MnO2ordered mesoporous carbon. Since electrolyte
diusion within the bulk electrode materials is a rate-limiting
step, a crucial issue to improve the rate capacity of ECs is to
optimize the electrolyte transport paths without sacricing
electron transport. Ordered mesoporous carbon materials
are another attractive type with a nanostructured hierarchy
with desirable electrolyte transport routes. Ordered mesoporous
carbon can be synthesized through the carbonization of
carbon precursors inside silica or aluminosilicate mesoporous
templates, followed by the removal of the templates.229233
Dong et al. presented a novel MnO2/mesoporous carbon
composite structure, synthesized by embedding MnO2 into
the mesoporous carbon walls through the redox reaction
between permanganate ions and carbons (Fig. 30a).229 A large
specic capacitance, as high as 200 F g 1 for the MnO2/
mesoporous carbon composite and 600 F g 1 based on MnO2
content, was achieved with high electrochemical cycling
stability.229 A similar process was applied to obtain Mn2O3templated mesoporous carbon composite electrodes.231 A
specic capacitance of over 600 F g 1 in term of manganese
oxide and a volumetric specic capacitance of 253 F cm 3 were
realized in the composite electrodes. Good capacity retention
of over 85% was achieved by the composite electrode after
800 chargedischarge cycles.231
Three dimensional (3D)-assemblies of silica spheres were
used as a hard template to synthesize porous carbon materials
with large mesopores (B100 nm) and large surface areas
reaching up to 900 m2 g 1.232 Birnessite-type MnO2 was
deposited by a chemical co-precipitation method in the porous
network (Fig. 30b).232 With increasing MnO2 content, the
specic surface area decreases steadily, while the specic
capacitance increases rst and then decreases if the MnO2
loading is higher than 10 wt%.232 This behavior can be
explained as follows. Below the 10 wt% MnO2 threshold, all
precipitated MnO2 particles have ecient electrical contact
Chem. Soc. Rev., 2011, 40, 16971721
1717
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Fig. 30 (a) Novel MnO2/mesoporous carbon composite with MnO2

embedded into the mesoporous carbon walls; (b) MnO2 deposited by a
chemical co-precipitation method within porous carbon materials with
large mesopores. (a, reproduced from ref. 229, reprinted with permission.
Copyright 2006, American Chemical Society; b, reproduced from
with the carbon surface for a good quality electro-active

material/substrate solidsolid interface.232
3.3.5 Summary of MnO2nanostructured carbon composites.
As described above, nanostructured carbons such as CNTs,
nanographites, carbon nanofoams, and ordered mesoporous
carbons are widely used as high surface area and excellent electron
conducting architectures for MnO2-based composite electrodes.
In a mild alkaline salt solution, although nanostructured
carbons generally exhibited very low specic capacitance, the
capacitance with respect to MnO2 increased linearly with
the content of nanostructured carbons. This implies that the
utilization ratio of MnO2 increased mainly due to the enlarged
contact area between MnO2 and the electrolyte and the higher
electrical conductivity induced by highly porous and conductive
nanostructured carbons. It is noted that the nanostructured
carbons produced under dierent synthesizing conditions
exhibit a variety of physicochemical features and electrochemical properties. For instance, CNTs can have dierent
wall numbers and defect densities; mesoporous carbons may
show large variations in pore size and overall porosity, so a
comparison between electrodes consisting of various kinds of
nanostructured carbons is rather tricky.
Major technical drawbacks for MnO2nanostructured
carbon composite materials are the relatively low mass loading
of MnO2 and its low density. MnO2 loading has to be
optimized to achieve high specic capacitance without increasing
the charge-transfer resistance or blocking the electrolyte
transport within the composite electrodes. Moreover, in the
literature, the specic capacitances of such composite materials
are typically reported in the gravimetric form (F g 1), while
volumetric energy density (F cm 3) of the composite materials
could be more important in terms of commercial applications.
The low packing density of the composite electrodes comprising
porous nanostructured carbons bottlenecks the volumetric energy
density since a large proportion of inactive components is used.
4. Concluding remarks
The full potential of manganese oxide-based electrochemical
supercapacitors has not been realized yet, as outlined in the
present review; however, a solid groundwork for future technical
advancements has been established. Innovative manufacturing
1718
Chem. Soc. Rev., 2011, 40, 16971721
processes have been developed to make chemical and structural

modications to manganese oxide materials to introduce more
electrochemically active sites or to shorten the transport path
length for both electrons and cations. This is achieved by using
porous, high surface area, and electronically conducting
carbon architectures. The low chemical and structural stability
and exibility of active materials can be improved through the
formation of manganese oxidepolymers composite materials.
However, it is noted that very little systematic work has been
done on optimization of the chemistry and microstructure
of the many composite electrodes described above. Many
fundamental questions remain unanswered, particularly regarding
characterization and understanding of electron transfer and
atomic transport during the electrochemical interface processes
within the composite electrodes. The authors believe that, in
order to fully exploit the potential of manganese oxide-based
electrode materials, it is critical to optimize both synthesis
parameters and material properties.
In addition to the materials issues related to electrode
development, the engineering of electrodes is an important
factor which is not well established in the literature. Electrode
materials with well-designed 3D architectures are vital to
achieve high energy/power densities in electrochemical supercapacitors. Furthermore, the selection of counter electrodes,
electrolytes (such as divalent cation-containing solutions,
hydrogel polymers, and ionic liquids), membrane separators,
current collectors, and packaging, as well as other practical
issues that aect the overall cell performance, need to be
intensively investigated.
Acknowledgements
The authors acknowledge funding contributions from the
Natural Sciences and Engineering Research Council (NSERC)
of Canada and Versa Power Systems (VPS).
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