REVIEW

Manganese oxide based materials for

supercapacitors
S. W. Zhang and G. Z. Chen*
Manganese oxides, as an environmentally friendly material with various oxidation states, have a
long history as an electrode material for batteries. Recently, a new energy storage system,
supercapacitor, with its unique power density and energy density range, has been put in the
focus. With a vast number of ongoing researches in exploring the MnOx as the electrode materials
Published by Maney Publishing (c) IOM Communications & W S Maney & Son Ltd

for supercapacitors, this article provides a comprehensive review on the recent findings in this
area. Different approaches to synthesise and the electrochemical behaviours of various forms of
pure and composite MnOx were presented. Important parameters that can influence the
electrochemical behaviour of manganese oxides based materials are summarised. The state of
the art of engineering of MnOx into composites or specific nanostructures with improved
electrochemical performance is reviewed. A brief survey on the performance of symmetric and
hybrid supercapacitors with MnOx as electrode material is given and appropriate cell
configuration has been proven to be necessary for the optimisation of the capacitive
performance. Moreover, the essential difference of charge storage mechanism between battery
and supercapacitor for MnOx electrode is stated. Based on these literature findings, MnOx is
believed to be a type of promising and competitive electrode material for applications in
supercapacitors.
Keywords: Manganese oxides, Supercapacitor, Charge storage mechanism, Nanostructure, Cell performance

Introduction other hand, as the twelfth most abundant element on the

In the context of fossil fuel shortage and climate change,
the production, conversion, storage and distribution of
energy have become the focus of todays world. Owing
to its unique power density and energy density range
which fills the gap between batteries and traditional
capacitors, supercapacitors (also known as electroche-
mical capacitors or ultracapacitors) play important roles
in energy storage and efficiency.13 Typical electrode
materials for supercapacitors include carbon, conduct-
ing polymers and transition metal oxides.1 Reviews on
supercapacitors based on carbon materials4,5 and con-
ducting polymers6,7 have been published elsewhere.
Metal oxides represent a type of attractive material with
high specific capacitance, wide operational potential
window and stability through chargedischarge cycling.
Ruthenium oxide (RuO2), as an early example, can
deliver relatively constant and appreciable capacitance
of 6001000 F g21 (Ref. 8) with a potential window of
1?4 V. However, the rarity of ruthenium in the earths
crust and hence the high market price of RuO2 limits
applications mostly in military and aerospace.1 On the
Department of Chemical and Environmental Engineering, Faculty of
Engineering, University of Nottingham, University Park, Nottingham NG7
2RD, UK
*Corresponding author, email george.chen@nottingham.ac.uk
earth,9 manganese is an inexpensive material with
various oxidation states. Manganese oxides (MnOx)
are a class of environmentally friendly material com-
pared with other metal oxides, only harmful by excessive
inhalation or imbibing.9 Throughout the years, MnOx in
various forms has been widely studied as the electrode
materials in various energy storage systems, such as
alkaline batteries, lithium ion batteries and supercapa-
citors. In all these cases, MnOx has been proven to be a
reliable electrode material with high performance.
This paper reviews recent research works carried out
in relation to MnOx, including the different approaches
to synthesis, the critical parameters affecting the
electrochemical characteristics and the possible techni-
ques for improved supercapacitor performance. More
specifically, recent investigations in the charge storage
mechanism of MnOx are reviewed and a hypothesis of
the origin of the pseudocapacitance is proposed. This
review, however, does not place the emphasis on specific
capacitance because in different research groups, the
thickness of the electrode differed, the content of
manganese oxides in the electrode varied and different
electrolytes were applied. These critical factors are
determinants for the electrochemical performance of
MnOx. More often than not, the specific capacitance was
calculated based on the weight of hydrous manganese
oxide only, regardless of the percentage of the hydrous

2009 Institute of Materials, Minerals and Mining

and W. S. Maney & Son Ltd
Received 4 December 2008; accepted 25 January 2009
186 Energy Materials 2008 VOL 3 NO 3 DOI 10.1179/174892409X427940
 Zhang and Chen Manganese oxide based materials for supercapacitors
Published by Maney Publishing (c) IOM Communications & W S Maney & Son Ltd

ac MnO2 in different electrolytes in range from 20?2 to 1?0 V v. Hg/Hg2Cl2;10 d effect of scan rate on cyclic voltammo-
grams of MnO2 in 2 mol dm23 KCl solution at 25uC;11 e impedance characterisation of amorphous MnO2 in absence and
presence of single walled CNTs in 1?0 mol L21 Na2SO412
1 Electrochemical characterisations of manganese oxides

manganese oxide in the composite, which makes such Mn(IV)/Mn(III) and Mn(VI)/Mn(IV) within the poten-
calculations less meaningful in practical application. tial window of water decomposition.13,14 As depicted in
Fig. 2,15 the thermodynamic equilibriums of various
Mechanism of charge storage manganese oxides are dependent on the potential and
the pH of the system.
As presented in Fig. 1, within a certain potential range, The two accepted hypotheses for charge storage
MnOx can exhibit, in good approximation, rectangular mechanisms of manganese oxides in supercapacitors
cyclic voltammograms (CVs). Such behaviour differs were proposed to be surface adsorption of electrolyte
from many usual charge transfer reactions on electrode, cations (Mz) on MnO210 (equation (2)) and proton
but it is in fact Faradaic in nature, i.e. the electrode intercalation (equation (3)).16 It was further suggested
processes involve electron transfer across the electrode/ that both protons and alkali cations are involved in the
electrolyte interface. However, the CVs also resemble in redox process,17,18 if the structure of the manganese
shape what is usually observed during the so called oxides (MnOx) is not too dense for the diffusion of alkali
electrode double layer chargingdischarging process in cations.19 A more specific statement was made that
which electrons and ions are only accumulated on each
side of the electrode/electrolyte interface (like that in a
capacitor as discussed in more detail below). There are
many other materials such as polypyrrole and RuO2 that
behave very similarly as the MnOx used to record the
CVs in Fig. 1 and such charge transfer related capacitor
like behaviour has been generally described as pseudo-
capacitive. The associated capacitance value, i.e. the
pseudocapacitance, can be derived from the CV data
using equation (1) below1
Dq dq=dt I
C~ ~ ~ (1)
DE dE=dt v
where i is the current and v is the potential scan rate.
In general, the pseudocapacitance of hydrous manga-
nese oxides is attributed to the redox transitions of
interfacial oxycation species in various oxidation
states.13 These redox transitions of hydrous manganese 2 PotentialpH diagram of manganese in aqueous solu-
oxides include the transitions between Mn(III)/Mn(II), tions at 25uC14

Energy Materials 2008 VOL 3 NO 3 187

 Zhang and Chen Manganese oxide based materials for supercapacitors
3 Comparison of cyclic voltammograms at different scan rates of a ideal capacitor derived from equation (1), or deloca-
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lised pseudo-capacitive electron transfer in semiconductors, and b ideal localised reversible charge transfer reaction
in thin redox active coating on electrode, derived from equation (4)
H3Oz plays the predominant (.60%) role in all cases,
while the extent of participation of alkali cations first
decreases and then increases with ionic size,20 based on
the research on finely grained MnO2.nH2O thin film with
j-MnO2 type crystal structure in several aqueous alkali
and alkaline salt solutions
(MnO2 )surface zMz ze{ '(MnO2 { Mz )surface
where Mz5Naz, Kz, Liz 10
represented in18
Positive electrode
MnOOH'H1{d MnO2 zdHz zde(0vdv0:5)
Negative electrode
MnO2 zdHz zde'Hd MnO2 (0vdv0:5)
It is to be noted that MnOx has been widely used as an
electrode material in both batteries and supercapacitors.
The electrode reactions remain the same or similar in
both devices, as described by equations (2) and (3).
However, in supercapacitors, the loading of MnOx on
each electrode is usually less than a few tens of mg per
cm2 in mass or a few tens of mm in thickness. The
consequence is that, in comparison with batteries,
supercapacitors have a smaller charge storage capacity,
but a greater overall charge transfer rate to enable high
power performance.
Another important electrochemical feature of MnOx
is its capacitor like chargedischarge characteristics, i.e.
the extent of charge acceptance Dq changes linearly, or
almost linearly, with the change of potential DE.1 This
behaviour is described by equation (1).
Note that the polarity of the current is determined by
the direction of the potential scan. For a constant C,
equation (1) leads CVs in the rectangular shape as
shown in Fig. 3a, which can be compared very fairly
well with the CVs in Fig. 1a and d for MnOx. However,
not all redox active materials can respond to potential
change as a capacitor. For example, according to
Ref. 21, for the thin layer of a redox active material
that is chemically bonded to the surface of an electrode
and undergoes the reversible electron transfer reaction
R=Ozne, the currentpotential plot is typically bell
188 Energy Materials 2008 VOL 3 NO 3
shaped with the peak potential determined by the redox
potential of the material (Fig. 3b). In this situation, the
current response towards the potential change is
expressed as21
n2 F 2 ACt v exp(E{E o )(nF=RT)

i~ (4)
RT f1zexp(E{E o )(nF =RT)
g
(2) where n is the number of electrons transferred between
the reduced and oxidised sites, Ct (5CozCr) is the total
surface covered by the reduced and oxidised sites and A
is the area of electrode. Assuming that n51, A51 cm2,
Ct50?05 and T5300 K, the CVs calculated from
(3a) equation (4) at three different scan rates are presented
in Fig. 3b.
Equation (4) and Fig. 3b are the basis of a large
family of functionalised electrodes known as the
(3b) chemically modified electrodes.21 Clearly, the electrode
processes represented by Fig. 3b differ significantly from
that represented by Fig. 1ad which are closer in shape
to the CVs in Fig. 3a. The reason for these two very
different CV shapes, both of which are faradaic in
nature, can be explained below, considering localised
and delocalised valence electrons.
Basically, the electron transfer processes in the classic
chemically modified electrodes take place in very well
separated redox active sites which are non-interactive
with each other. In other words, these localised redox
active sites are equal or fairly close to each other in
energy state, and hence accept or donate electrons at
potentials very close to each other, leading to the peak
shaped CV in a narrow potential range. However, if
these redox active sites are closely located in the surface
layer of the electrode and hence interactive with each
other, a broad range or band of energy states can form
with negligibly small differences between the neighbour-
ing states. Such a situation corresponds that in
semiconductors, including most transition metal oxides,
and is also comparable with electron delocalisation in
conjugated chemical bonds, as in conducting polymers,
resulting from overlapping electron orbits between
neighbouring atoms. Consequently, electron transfer
into each energy state in this broad band becomes
continuous over a wide range of potentials, which is
responsible for the constant current flow and hence the
rectangular CV.

4 Schematic illustration of band theory21
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The above analysis is derived from the semiconductor
or band theory21 which is qualitatively illustrated in
Fig. 4. The right hand side of Fig. 4 represents the
electron energy states in isolated molecules and insula-
tors, and can be compared with the classic chemically
modified electrodes in which the redox active sites are
well separated and only support localised electron
transfer from the electrode substrate to each of the
redox active sites and vice versa, but no electron
conduction between any neighbouring sites. The energy
levels of the filled and vacant states are singular,
corresponding to a fixed potential for electron transfer.
The far left hand side of Fig. 4 shows the continuous
electron energy states from the fill valance band to
vacant conduction band, enabling free electron mobility
in response to an electrical field. In Fig. 4, semiconduc-
tors are featured by the separated filled valence band
and the vacant conduction band. The energy gap
between the lowest vacant and highest valence levels
Eg is characteristic to each semiconductor. In a
sufficiently high and increasing electrical field, contin-
uous excitation of electrons from the valance band to the
conduction band occurs. This process produces free
moving or delocalised electrons in the conduction band
as well as mobile holes in the valence band,21 leading to
the continuous charge accumulation upon the applica-
tion of the increasing potential, and hence the capacitive
current.
Figure 4 also shows the so called Fermi level EF,
where the probability of occupancy of the energy state
by electrons is 0?5.21 At any other energy levels E, the
probability of occupancy is governed by the Fermi
function f(E), as given below
  
(E{EF ) {1
f(E)~ 1zexp (5)
kT
where k is the Boltzmann constant and T is the absolute
temperature. From the Fermi function, it can be easily
deducted that for the energies much lower than the
Fermi level, the occupancy is practically 1, and for
energies much higher than the Fermi level, the occu-
pancy is 0.21 Neither of these two situations can facilitate
the mobility of electrons. Only for the energy states
within a few kT of EF have intermediate occupancy
which can contribute to the electrons mobility. Thus the
potential range within which the capacitive behaviour
occurs is restricted.
Zhang and Chen Manganese oxide based materials for supercapacitors
Advanced technologies, including X-ray photoelec-
tron spectroscopy (XPS), X-ray absorption near edge
structure (XANES) technology and K edge X-ray
absorption spectroscopy, have made it possible to
identify the exact oxidation status and study the
pseudocapacitive nature of charge storage in MnOx. A
progressive change of the Mn valence was observed
when the potential decreased from 1?0 to 0 V 20 and the
hysteresis of Mn oxidation state adjustment with respect
to the applied potential was also revealed.22 Manganese
oxidation states for the reduced and oxidised forms
during the charge/discharge process have been identi-
fied19,18 and more explicit observations of a continuous
and reversible change in Mn oxidation state, from
z3?23 to z3?95 and then back to z3?27 with potential
cycling, were reported.22
It is worth pointing out that deviation from the band
theory can occur if the electrode process involves kinetic
complications, for example, the influences of counter ion
diffusion and ohmic polarisation. Thus, MnOx in the
form of a thin coating, particularly porous, can behave
like a capacitor. However, when it is used in a bulk
quantity in batteries, the performance is largely con-
trolled by the diffusion of the counter ions, and hence
deviates from that of a capacitor.
Synthesis of manganese oxides
Chemical synthesis
Common chemical approaches to MnOx include redu-
cing Mn7z to Mn4z in solution with low pH23 by agents
like CH3CH2OH in acetonitrile24,25 and oxidising Mn2z
to MnO2 by agents like BrO32 and S2O822.26,27 By
altering the pH of the starting solution, various products
including Mn3O4, b-MnOOH and c-MnOOH can also
be obtained.26
Another useful and effective approach to synthesise a-
MnO2 is using Mn2z to reduce MnO42, e.g. adding
MnSO4 into KMnO4 solution16,17,28 or mixing KMnO4
and manganese(II) acetate solutions in water.10,29,30
Such reactions are generalised in equation (6)10,28
2MnO4 { z3Mn2z z2H2 O
(6)
'5MnO2 z4Hz
4KMnO4 z3Cz2H2 SO4
(7)
'4MnO2 z3CO2 z2K2 SO4 z2H2 O
It is worth mentioning that MnO42 can be reduced by
carbon and form a uniform coating of MnOx onto, e.g.
the surface of a graphite electrode through one step
reaction in an acidic solution,31 as in equation (7). This
inspiring discovery suggested a simple route in synthe-
sising various MnO2/carbon composites, including
carbon nanotubes (CNTs),32,33 activated carbon materi-
als34 and exfoliated graphite plates.35
Electrochemical synthesis
A prominent advantage of synthesising MnOx through
electrochemical deposition is that the product will be in
the form of a homogeneous thin film on a conducting
substrate, i.e. graphite, stainless steel, titanium foil, etc.,
without using any type of binder. This can largely
improve the situation of a resistive electrode caused by
Energy Materials 2008 VOL 3 NO 3 189
 Zhang and Chen Manganese oxide based materials for supercapacitors

the aggregation of manganese oxide powders. The

reaction of electrochemical deposition is represented in
equation 836
Mn2z z2H2 O'MnO2 z4Hz z2e{ (8)
Successful electrochemical depositions have been carried
out with various precursors, including manganese
acetate,11,36,37 manganese sulphate,3841 manganese
chloride,39 manganese nitrate, etc.;39 manganese acetate
was claimed to be a superior precursor among all39 due
to its high deposition rate at much lower potentials39
and the existence of acetates having offered a more
controllable reduction in the deposition potential.38
However, the capacitive performance is independent of
precursors as the mean oxidation state of Mn is not
significantly affected by changing the anions of manga-
5 Patterns (XRD) of a b-MnO2, b c-MnO2 and c porous a-
nese precursors.39 Different electrodepositing condi-
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tions, galvanostatic, potentiostatic and
potentiodynamic conditions, were compared40 and the
potentiodynamic deposition was claimed to be able to
produce superior MnO2 with optimum capacitive
behaviour.
The deposition condition and deposition potential
have been proved proven to have profound influence on
the oxidation state of manganese,11 the nanostruc-
tures,36 BET surface area42 and eventually electroche-
mical performance of the product. On average, the
specific capacitance of the MnOx synthesised from
electrochemical deposition is slightly above 200 F g21,
when the thickness of the film is of several tens of
nanometre.42 However, this figure could drop drastically
to y50 F g21 when the thickness increases.38
Another interesting finding is that electrochemical
oxidation can be an effective method to convert non-
capacitive manganese metallic compound43 and crystal-
line oxides Mn3O44447 into capacitive MnOx in aqueous
solutions. The transformed MnOx was confirmed to be
the layer structured birnessite.45 High capacitance of
600700 F g21 was reported for a 20 nm thin film with a
low current density of 160 mA cm22.43 A high scan rate
of 500 mV s21 was achieved, resulting in a capacitance
of 170 F g21.46 An obvious advantage of this discovery
is that it separated the coating process from the
activation process; thus convenient techniques like
sputtering43 and electrostatic spray47 can be employed
to produce homogeneous thin film at large quantity with
low cost. However, for thin films synthesised in this
manner, the thickness, corresponding to the electrolyte
accessibility, remained a limiting factor for the capaci-
tance and the maximum achievable capacitance reported
was 50 mF cm22.43
Solgel route
Solgel route is based on the hydrolysis and condensa-
tion of manganese ions. It was developed with the aim of
producing colloidal sols containing nanoparticles which
can be deposited as very thin porous films on a substrate
via dipping or spinning procedures.48 Results from
various research groups have shown that homogeneous
and highly porous MnOx powders with particle size of
submicron metres can be synthesised through this route.
Often, Mn7z is reduced into amorphous MnO2 by
fumaric acid.48,49 The particular reaction is presented in
equation 9.5053
MnO262
3C4 H4 O4 z10KMnO4 '10MnO2
(9)
z3K2 C2 O4 z4H2 Oz4KOHz6CO2
Drying the MnOx gel at room temperature can produce
a densified xerogel of MnOx.54,55 However, xerogel has
exhibited less satisfying capacitive behaviour compared
with porous hydrous MnOx films and underwent severe
capacity loss of 50% after eight chargedischarge
cycles.54
It is also reported that a stable colloidal MnOx, with a
high concentration of MnOx, can be prepared by
reduction of tetraalkylammonium (methyl, ethyl, propyl
and butyl) permanganate salts in aqueous solutions with
2-butanol and ethanol.56 This solgel derived tetrapro-
pyammonium MnOx thin film on nickel substrates
exhibited good electrochemical behaviour.57
Important parameters influencing
pseudocapacitive performance
Electrode property and treatment
Crystalline structure
In nature, MnOx have a number of polymorphs with
many types of tunnel and layered structures.58 The XRD
patterns of several commonly occurred MnOx are
presented in Fig. 5. Crystalline structure has been found
to have profound impacts on the electrochemical
performance of the MnOx;50 by transforming distorted
spinel Mn3O4 to layered structure birnessite through
potential cycling in aqueous Na2SO4, an increased
capacitance of more than 20 times of the value of the
original spinel Mn3O4.44,45,47 Early researchers, how-
ever, showed more interests in amorphous MnO2 and
nanocrystalline compounds for the application in
electrochemical capacitors,10,13,59,60 with the belief that
a porous morphology can enhance the ion accessibility
and cation diffusion. Nevertheless, the poorly crystal-
lised MnO2 contains intergrowth of different tunnel
structures, leading to more difficult cation diffusion and
resulting in higher resistance.50 The maximum capaci-
tance of this type of materials is limited by the upper
limit of BET surface area it can achieve.
Recently, several attempts have been made to explore
the crystallised MnO2 materials.50,61,62 Various types of

190 Energy Materials 2008 VOL 3 NO 3


MnO2, including a-MnO2, b-MnO2, c-MnO2, d- MnO2,
with one-dimensional and three-dimensional tunnel
structures, and birnessite j-MnO2 with layered struc-
ture, have been tested for possible applications as the
cathode material.50,58 It was reported that for MnOx
with various crystalline structures, the birnessite materi-
als doped with potassium with two-dimensional struc-
ture is at advantage as the presence of Kz ions inside the
two-dimensional tunnels allows the participation of a
larger fraction of the MnO2 to the charge storage
process; while the specific capacitance of materials with
one-dimensional tunnel structures is generally low, e.g.
c-MnO2 of 30 F g21 and b-MnO2 merely 5 F g21,
because of slow cation diffusion which limited the
charge storage processes to the surface.50
A more fundamental reason is that the structure
change also leads to significant change in conductivity,63
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which eventually influences the pseudocapacitive beha-
viour. Owing to the JahnTeller distortion of the
Mn(III)O6 octahedron, the conductivity of MnOx
involving trivalent Mn(III) is rather low as compared
to that of MnO2 or amorphous manganese (oxyhydro)-
oxides involving Mn(IV).63 When transforming thermo-
dynamically stable c-Mn2O3 into a-Mn2O3 and Mn3O4
by mechanical grinding,63 it was discovered that the
capacitance of MnOx decreased linearly with decreasing
crystallinity of c-MnO2 due to the formation of
Mn(III)O6 octahedron.63
Thus, it can be concluded that although the majority
attention is still focused on the study of amorphous
MnOx, crystalline MnOx with suitable tunnelled struc-
tures represents a group of rising candidates for the
electrode materials in supercapacitors.
BET surface area and pore structures
In general, larger surface area indicates higher accessi-
bility of the active materials, leading to a better
capacitive behaviour. Several research projects focusing
on synthesising MnO2 with larger effective surface area
have yielded encouraging results.29,64,65 Efforts have
been made to enhance the surface area and porosity of
MnOx films by adding surfactant, sodium lauryl
sulphate64 and Triton X-100 during electrodeposition.65
Enhanced surface area of 76?4 and 84?46 m2 g21 were
reported with the addition of these two surfactants
respectively, corresponding to 20 and 60% of improve-
ment in specific capacitance. On the other hand, a fade
of 40% in capacitance has been reported due to a 50%
decrease in surface area from the aging of the
coprecipitated MnO2.50
However, it was suggested that for amorphous MnO2,
the capacitance reaches a maximum at a surface area of
200 m2 g21, further increase in the surface area does not
provide additional charge storage.50 Moreover, it was
claimed that specific capacitance depends on the pore
size distribution rather than BET surface area.55 Since
the functions of pore size and pore structure on the
double layer capacitive processes have been well
studied,1,66,67 it is worthwhile to extend the research
into the process of pseudocapacitance.
Based on the transmission line model,68,69 mathema-
tical models considering the effect of the pore size
distribution for the impedance of porous materials have
been developed67,70 with various research findings to
complement the understanding. It was observed that for
the two types of MnOx, in the forms of xerogel and
Zhang and Chen Manganese oxide based materials for supercapacitors
ambigel, with similar surface areas of 63 and 72 m2 g21
respectively, the xerogel only exhibited 56% of the
capacitance of ambigel. As the majority of the pore
diameters of xerogel are ,20 nm, while ambigel are
mesopores with diameters of 20100 nm.55 Similar
conclusion that a higher percentage of large pores can
ensure the delivery of higher power at higher charge/
discharge rate was also drawn from the MnOx film
synthesised by potentiostatic deposition.42 Moreover,
three types of porous MnO2, ordered mesoporous b-
MnO2 with [161] channels, disordered mesoporous c-
MnO2 with [162] and [161] channels and disordered
porous a-MnO2 with [161] and [262] channels, were
synthesised to study the relationship between electro-
chemical properties and pore structures of MnOx.62 It
was declared that the capacitance profiles of the three
types of one-dimensional tunnel structure MnO2 are
clearly dependent upon the pore structure despite of
their crystalline structures. Mesoporous, especially
ordered mesoporous MnO2, has superior capacitive
performance, rate capability and high frequency perfor-
mance in 1M Na2SO4 solution due to its lower pore
resistance and its better accessibility of ions to the
electrochemically active surface.62
Thus, it is to conclude that surface area as well as the
pore structures is the determinant factors for the
accessibility of the MnOx to the electrolyte, which limits
the depth and rate of ions transfer within the bulk
materials. Engineering MnOx with desirable structure of
organised mesopores and macropores may enhance the
overall capacitive performance.
Thickness and loading of manganese oxides
Thickness is a key limiting factor for the capacitive
performance of MnOx materials. Significant decrease in
specific capacitance with increasing electrode thickness
has been reported by most research groups, disregarding
whether the material was synthesised by electrodeposi-
tion, solgel route or chemical deposition.
Often, exceedingly low loading of the MnOx was
applied onto the electrode to ensure a high specific
capacitance, on the order of tens of mg per
cm2,47,64,65,71 or with a thickness of tens of nano-
metres.42 In such cases, e.g. at the loading of
0?03 mg cm22, even an extreme high specific capacitance
of 1330 F g21 would only provide an electrode capaci-
tance of 0?039 F cm22,64 which is of little use for real
world application with high power and energy demand.
Even at low loading, the decreases in specific capacitance
with increasing the loading are discernable. A 55%
decrease in its initial specific capacitance of 330 F g21
was reported when the loading was increased from 18 to
116 mg cm22 for the thin layer of MnOx obtained from
electrostatic spray deposition;47 similar observations
were made with MnO2 obtained from chemical deposi-
tion71 and electrodeposition.38
Essentially, this limiting effect of the thickness of the
MnO2 loading is the combined results of the low
electrical conductivity of MnOx, the obstruction from
the longer path for the diffusion of protons.13,39 and
other ions.17 It was also suggested that only a limited
fraction of the MnO2 composite is electrochemically
active.17,18,50,61 K0?02MnO2H0?33.0?53H2O was fabri-
cated into films of different thicknesses (,5100 mm).18
No change of the manganese oxidation state was
detected for the inner layer of the thicker film electrode,
Energy Materials 2008 VOL 3 NO 3 191
 Zhang and Chen Manganese oxide based materials for supercapacitors

a finding totally different from the case of thin film

electrode. Besides, the specific capacitance obtained so
far are still far from the theoretical value of more than
1000 F g21,64,72 which implies the existence of a vast
amount of material that has not been utilised.
However, amelioration has been proved effective in
improving the situation. For example, introducing
CNTs into the MnOx during synthesis can form a
three-dimensional porous and conducting network of
CNTs to assist the electron and ion transfer within the
MnOx. A electrode capacitance of 5 F cm22 at high
loading of 35 mg cm22 was achieved in this manner.32
Various attempts to overcome the limitations of the
thickness have been made, many of which have achieved
encouraging results.
Annealing temperature
A number of studies have been carried out about the
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effects of annealing temperature and annealing time on

the electrochemical activity of MnOx. Essentially,
annealing treatment results in three transformations
in the manganese oxides: loss of water content,
decrease in surface area and changes in structure.
The effects of annealing on these aspects will be
discussed in detail.
Water content in MnO2 is known to affect the
electrochemical reactivity and thermodynamic stability
of various MnO2 phases as it causes a variation in
crystal lattice and a consequent variation in electrical
conductivity and electrode potential.16 Heat treatment
at a temperature up to 200uC is believed to remove both
physically and chemically adsorbed water molecules.17
The loss of water molecules means a reduced weight,
which may lead to a small increase in specific
capacitance;17 however, it also leads to a decrease in
surface area,73,17 which can vitally hinder the electro-
chemical activity. Furthermore, chemically bound water
is believed to be essential for the transportation of active
ionic species. Consequently, the loss of water content
through heat treatment will lead to the loss of
pseudocapacitance (as explained in the section on
Mechanism of charge storage).40,74,75 It was suggested
that similar to the case of ruthenium oxides,74 the
increase in water content leads to increase in ionic
transport while the decrease in electronic transport at
the same time.40 Thus, heat treatment up to a certain
level can possibly enhance the overall pseudocapacitive
behaviour,16,57 although most researchers observed
monotonic decrease in specific capacitance upon heat
treatment even at temperatures below 200uC.17,73,7678
Significant structure changes, together with a drastic
decrease in surface area, will occur at an annealing
temperature above 300uC (Fig. 6.).79 As described in the
section on Crystalline structure, certain crystalline
structures of MnOx are less favourable for the charge
storage mechanism; transition into one of these crystal-
line structures will definitely diminish the pseudocapa-
citance of the electrode material. The transformation
from amorphous and hydrous MnOx to Mn3O4 and
Mn2O3 with crystalline structures was observed upon
the increase in annealing temperature up to
600uC.17,76,80 Condensation, rearrangement, reconstruc-
tion and growth of the deposited MnOx as a function of
temperature were recognised by atomic force micro-
scopy during annealing.76 It was concluded that heat
treatment at temperatures higher than 200uC will
a as prepared; b 3 h at 300uC; c 3 h at 450uC; d 3 h at
600uC
6 Crystalline structure transition of a-MnO2 upon anneal-
ing treatment79
promote the formation of crystalline Mn3O4 and
Mn2O3 and consequently result in the loss of pseudo-
capacitive properties of the oxides.17,76,80
The corresponding decrease in BET surface area upon
the transition from a-MnO2 to Mn2O3 through anneal-
ing from 70uC to 800uC was also reported.73
Deterioration of a-MnO2 with tetragonal unit cell
structure was observed with increasing annealing tem-
perature, especially at temperatures higher than 300uC;
and a continuous decrease in BET surface area, from
initially 190 to 145 m2 g21 at 300uC and finally 8 m2 g21
for the Mn2O3 annealed at 600uC and above,73 was
attributed to agglomeration of particles on annealing.
The corresponding degradation in capacitive perfor-
mance was observed, with a loss of 13% of its specific
capacitance upon annealing at 200uC, due to the loss of
water content, and a further drastic 63% loss at the
annealing temperature above 400uC, due to the transi-
tion from a-MnO2 to Mn2O3.73
In order to gain a clear understanding of the phase
and phase evolution involved in MnOx materials during
the thermal treatment, an in-depth microstructural
characterisation of manganese oxide materials formed
from the physical vapour deposition process was
conducted.77 The cubic forms of Mn and MnO with a
porous zigzag structure were formed from e-beam
evaporation and deposition. Upon annealing at 300uC,
Mn is progressively oxidised to MnO, followed by
further oxidation of MnO to Mn3O4. The zigzag
structure near the surface was thus destroyed and
replaced with a columnar oxide layer of cubic MnO
and tetragonal Mn3O4. This capping effect ultimately
reduces the usable surface area and is thought to
account for the reduction in capacitance seen on
annealing.77 Further research81 confirmed that the
thermally annealed sample did not contain hydrated
manganese (MnOH), but only anhydrous compounds
(MnOMn) and free water (HOH), which is
believed to be the reason of its poor pseudocapacitive
performance.

192 Energy Materials 2008 VOL 3 NO 3


Electrolyte
The choice of electrolyte also has significant impacts on
the performance of the MnOx electrodes. The pH
condition is an important determinant of operating
potential window; and different existing ions determine
the rate of intercalation and the situation of corrosion.
Thus, desirable electrode performance can be obtained
by choosing the electrolyte carefully.
pH condition
As depicted in Fig. 2 (pHpotential performance),
electrochemical reversibility and the charge storage
mechanism of hydrous MnOx largely depend on the pH
of the electrolyte.13 Because Mn(II) and Mn(VII) are
soluble in the electrolytic solution, the reactions of
Mn(IV) to Mn(II) and Mn(IV) to Mn(VII) should be
avoided during charging and discharging the capacitor.
Published by Maney Publishing (c) IOM Communications & W S Maney & Son Ltd
These irreversible reactions will lead to partial dissolu-
tion of the electrode and a subsequent decrease in
capacitance and cycling reversibility.14,22,72 As pre-
sented in Fig. 2, the transformations of Mn(IV) into
Mn(II) and Mn(IV) into Mn(VII) occur at different
potentials under different pH conditions: the transfor-
mation of Mn(IV) into Mn(II) occurs at potentials of
0?47 and 0?05 V (v. NHE) for pH 6?4 and 10
respectively, and equilibrium potentials for the trans-
formation of Mn(IV) into Mn(VII) are 1?19 and 0?98 V
(v. NHE) for pH 6?4 and 10 respectively.72 Thus, by
optimising the pH, a maximum operation potential
window without incurring the dissolution of electrode
can be achieved.
On the other hand, it was suggested that the pH
condition affects the water decomposition and gas
evolution, which also limits the operating potential
window.82 Gas evolution reactions are related to H2O
decomposition, Hz reduction and OH2 oxidation
(equation (10)), the presence of excessive Hz ions
induces H2 gas evolution at 20?2 V, which limits the
operating voltage window to y1?2 V, while the
presence of excessive OH2 ions results in O2 gas
evolution at 0?7 V by their oxidation process, limiting
the operating voltage window to 1?8 V. An operating
voltage window of 2 V was achieved with the
1 mol dm23 KCl electrolyte in which the electrode
reactions for H2O decomposition were observed at
potentials of 1?1 V (anode) and 20?9 V (cathode) v.
Ag/AgCl reference electrode.82 The negative shift of
the cathode reaction potential was likely to be
responsible for the increased cell voltage (2?0 V) as
the result of a high overpotential for the hydrogen
evolution reactions, i.e. equations (10c) and (10d)
below, on the carbon material used in the cathode
2H2 O'O2 (g)z4Hz z4e{ (10a)
4OH{ 'O2 (g)z2H2 Oz4e{ (10b)
2Hz z2e{ 'H2 (g) (10c)
2H2 Oz2e{ 'H2 (g)z2OH{ (10d)
Ion size and intercalation
It was reported that electrolyte with equal transference
numbers for both cation and anion can promote
Zhang and Chen Manganese oxide based materials for supercapacitors
capacitive behaviour and anions with smaller hydration
sphere and smaller size leads to faster diffusion and
higher chemisorption rates.83 Experiments comparing
the electrochemical performance of the MnO2 material
in several neutral aqueous electrolytes including NaCl,
KCl and LiCl with the same concentration of
2 mol dm23 have been conducted.10,83 It was claimed
that although Liz is smaller than Naz and Kz, it has a
larger hydration sphere, which makes it disadvanta-
geous. And this theory was supported by the results
from several other research groups.31,55
However, a more recent study on the electrochemical
behaviour of the MnO2 electrode in 1 mol dm23 KOH
and 1 mol dm23 LiOH84 declared that the reaction
mechanism of MnO2 electrode in LiOH appears to be
Liz ion insertion/extraction in the MnO2 solid,
followed the battery reaction of MnO2zxLiz
zxe2=LixMnO2. This finding may elicit further
thoughts upon the mechanism of the charge storage
within MnOx.
Corrosion and non-aqueous electrolytes
Another major concern in selecting electrolyte is the
issue of corrosion. Although chloride solutions normally
have higher ionic conductivity which is desirable in
diminishing the iR drop, they are likely to cause
corrosion on stainless steel current collector.61 Thus,
platinum or titanium current collectors are normally
applied in chloride electrolytes. On the other hand,
sulphate based salts, although with lower ionic con-
ductivity and lower solubility, showed long term cycling
stability with stainless steel current collector.61 This
trade-off between ionic conductivity and corrosion
resistance is thus up to the individual researchers to
decide.
Alternatively, using an organic solvent provides a
solution for the corrosion issue. The electrochemical
performance of electrochemically deposited Mn3O4 in
degassed acetonitrile solution containing 0?1 mol dm23
TBAClO4 (TBA5tetrabutylammonium) and
0?2 mol dm23 H2O was studied.85 A 2 V potential
window was achieved; the presence of water in the
organic solvent facilitates the capacitive behaviour, yet
limits the potential window. However, the higher
resistance of the organic solvent impedes the capacitive
performance of the electrodes. The specific capacitance
calculated from organic solutions is only y60% of that
from aqueous solutions.85 Furthermore, a gel electro-
lyte of aqueous solution of KCl in potassium poly(-
acrylate) polymer with ionic conductivity in the order
of 1021 s cm21 was proposed to be used in the
MnO2.nH2O supercapacitor.86 It was reported that
the polymer component did not impose a negative
effect on leakage current and the supercapacitor with
the gel electrolyte in fact delivered substantially higher
specific capacitances than those in the liquid electrolyte
with the same salt (KCl) composition (1 mol dm23).
This improvement was attributed to the hydrophobic
nature of the polymeric component in the gel, which
enhanced the compatibility between the electrode
matrix and the electrolyte, and essentially increased
the wettability. On the other hand, the swelling process
of the polymer molecules within the electrode interior
can open closed pores which increased the electrolyte
accessibility.86
Energy Materials 2008 VOL 3 NO 3 193
 Zhang and Chen Manganese oxide based materials for supercapacitors
Engineering of manganese oxides for
improved performance
Composite materials
A composite that can retain the excellent properties of
each individual component and counterbalance the
shortcomings is always desirable. Various efforts have
been made to synthesise such composites of MnOx, with
the aim of overcoming the limitations stated in the
section on Important parameters influencing the pseu-
docapacitive performance.
With carbon
The relatively low electrical conductivity of MnOx limits
its loading and thickness as an electrode mate-
rial,29,85,87,88 which eventually limits the energy density
of the electrode and hinders its application in super-
Published by Maney Publishing (c) IOM Communications & W S Maney & Son Ltd
capacitor. Various methods have been developed to
overcome this shortcoming and the introduction of
carbon materials has been proven to be an effective
method to increase the conductivity. Different carbon
materials, e.g. carbon black, acetylene black, CNT and
exfoliated graphite, have been employed to form
composites with MnOx with the aim of promoting
conductivity and boost the utilisation of the redox
capacity of MnO2.
Activated carbon materials with high BET surface
area and excellent electrical conductivity represent a
good choice. Physically adding carbon to the MnOx has
long been employed to enhance electronic conductiv-
ity.10 In 2001, an attempt was made to obtain a MnOx/
carbon composite by adding carbon during chemical
synthesis of manganese oxide. The chemically coupled
carbon has been proven to be effective in increasing the
specific capacitance, improving electrochemical proper-
ties with reduced iR drop in high power mode compared
with physically mixed samples.29 Electrochemical synth-
esis of the Mn3O4/carbon composite, with improved
kinetic reversibility, was later realised in the same year,
from manganese halide complex LMnCl2 [L52,6-
(ArNCCH3)2C5H3N, M5transition metal atom] in
water containing acetonitrile electrolyte at room tem-
perature.85 Ultrasound irradiation synthesis of homo-
geneous amorphous sodium MnOx coating of 3 nm
thickness on acetylene black was also reported and the
composite exhibited good discharge capacity under high
current density.89 With the discovery that the direct
reduction of MnO42 on the surface of a graphite
electrode can result in a thin layer of MnOx deposit
with greatly improved performance related with charge
transfer kinetics,31 various MnO2/carbon composites
have been synthesised through chemical route with
satisfactory electrochemical performance.34
Carbon nanotube (CNT) is another favourite choice
(Fig. 7); the unique tubular structure is believed to be
able to produce consistent composites and an inter-
connected conducting network with high porosity for
enhanced electron transfer as well as electrolyte acces-
sibility.32 Various approaches have been made to
synthesise the composite of MnOx and CNTs: physical
mixing through ball milling,90 ultrasonic vibration
mixing,91 thermal decomposition,92 chemical codeposi-
tion,12,32,33,72,93 and electrochemical deposition.88,94
Although enhanced capacitive performance was
reported for composites synthesised with both multiwall
194 Energy Materials 2008 VOL 3 NO 3
a 50 nm; b 5 nm
7 Images (TEM) of MnOx/CNT composites from chemical
deposition55
CNTs and single wall CNTs,12 multiwall CNTs are a
more favourable choice. The enhancement, particularly
in the cases of thicker films,88 was attributed to the lower
resistance and larger surface area brought into the
composites by the CNTs.94 Moreover, the high entan-
glement of CNTs formed a network of open mesopores,
allowing the bulk of MnO2 to be easily reached by the
ions.72 It was claimed that compared with carbon black,
CNTs are a more effective additive in enhancing
conductivity of a-MnO2.nH2O.72 Extraordinary elec-
trode capacitance of 5?07 F cm22 was achieved on a
macroelectrode with the MnOx/CNT composites,32 and
the average specific capacitance of the MnO2/CNT
composites is expected to be in the range of 110
568 F g21,92 depending on the electrode fabrication.
Recently, novel approaches employing graphite plates
in the MnOx composites have been proposed. Exfoliated
graphite plates with their sheet like structures could be
more effective than small particles as conductive
material.35 Also, they are believed to offer larger contact
area between MnO2 and the electrolyte.95 Composites of
MnOx and graphite plates with competitive electroche-
mical performances have been successfully synthesised
through chemical deposition35 and the hydrothermal
route.95 And yet this type of promising carbon material
is to be further investigated.
With other metal oxides
Non-noble metal oxides, such as nickel oxide,96,97 cobalt
oxides98 and magnetite Fe3O4,99,100 have been individu-
ally studied as electrode materials and yielded positive
results. In general, these metal oxides have higher
electrical conductivity than MnOx, but with narrower
operating potential window and lower specific capaci-
tance. Therefore, by combining these complementary
metal oxides, it was hoped to promote desirable synergic
properties and functionalities and yield composites with
improved capacitive performance.
Cobalt oxides, with their so called intercalative
pseudocapacitance of Co3O4 and CoO2,101 are of
particular interests due to their good efficiency, long
term performance stability and the abundance in
nature.102 On the other hand, its non-constant capacitive
behaviour and small operation potential range (0?7 V)
are expected to be compensated by MnOx.101 Both
amorphous and crystallised (c-Mn12yCoyO22d) cobalt
MnOx composites have been successfully synthesised
through electrochemical deposition40,103,104 and hydro-
thermal route.105 The amorphous composites were
microporous40 and the addition of cobalt oxide was

claimed to be able to stabilise the MnOx at potentials
negative to 0 V,104 because cobalt oxide is inert in nature
and can suppress the dissolution of Mn into electro-
lyte.103 Excellent cycling stability and higher power
characteristics were recorded when characterised at a
high scan rate of 200 mV s21;40 however, higher Co
content was reported to cause a significant reduction in
the specific capacitance of the sample.103 The introduc-
tion of Co oxide into crystallised c-MnO2 of one-
dimensional tunnel structure with small tunnels has also
been proven to be effective in enhancing the capacitive
behaviour, due to the formation of a higher surface area
and a more favourable microstructure.105
Despite of the narrow operation potential window of
0?6 V, high specific capacitance of 240 F g21 has been
reported with nickel oxides from several research
groups.96,97 Moreover, nickel oxides have good electrical
Published by Maney Publishing (c) IOM Communications & W S Maney & Son Ltd
conductivity. Thus, the composites of manganesenickel
oxides were prepared by chemical reduction30 and
electrochemical codeposition40,106 to study the outcome
of the combination of these two. The composites showed
satisfying electrochemical behaviour, due to the con-
tribution of a large current response from nickel oxide106
and the increased surface area due to the formation of
micropores with the addition of nickel oxide.30
Iron oxides were also used by a few researchers as the
additional metal oxides for the MnOx. Fe/Mn binary
oxide film was synthesised onto a graphite substrate by
anodic deposition.107 X-ray photoelectron spectroscopy
(XPS), XANES and cyclic voltammetry revealed that
the incorporated iron presented as FeO, Fe2O3 and
FeOOH in the binary oxides. However, increasing the
amount of Fe in the binary oxides resulted in the
decrease in surface roughness and the specific capaci-
tance.107 MnFe2O4 nanocrystallites obtained from
coprecipitation of MnSO4 and FeCl3 in 1 mol dm23
HCl were also studied.108,109 In situ XANES and XRD
analyses demonstrated that the energy storage mechan-
ism of MnFe2O4 in aqueous solution is similar to that in
MnO2 rather than in Fe3O4. The redox reaction of the
ferrite phase involves charge transfer at both the Mn and
Fe ions over different potential ranges, balanced by
insertion/extraction of proton into/from the lattice.109
The MnFe2O4 nanocrystallite exhibited competitive
capacitive performance in both aqueous (NaCl)108 and
organic (LiPF6)109 electrolytes.
Other metals, including Pb,30 Al,105 Mo, etc.,19 in
their oxidised forms, have been combined with MnOx to
examine the resultant capacitive performance. In all
these cases, the composites were claimed to have
enhanced capacitive behaviour compared with MnOx
alone. The enhancements were largely attributed to the
formation of micropores,30 more favourable microstruc-
tures30,105 as well as the increase in electrical conductiv-
ity,19 even if the additional metal oxides did not
participate in the pseudocapacitive faradaic process.19
With conducting polymer
Conducting polymers are a type of attractive electrode
materials for supercapacitors. Continuous research has
been carried out to improve their electrochemical
behaviour through decades.6,7,110 Fast kinetics to the
doping/undoping mechanisms111 and highly promising
specific capacitance values, e.g. a value of 775 F g21
was obtained with polyaniline (PAni),112 have been
reported. In addition, the good electrical conductivity of
Zhang and Chen Manganese oxide based materials for supercapacitors
conducting polymers is believed to be beneficial to
improving the conductivity condition of MnOx.
However, conducting polymers suffer from the inade-
quacies of poor mechanical stability and a narrow
operating potential window, which limit their applica-
tion as an electrode material. Therefore, composites that
exhibit enhanced electrochemical activity are expected
by introducing conducting polymer into MnOx, if each
individual material can retain its electrochemical advan-
tage and be complementary to each other.
The composites of MnO2/PAni have been successfully
prepared through chemical codeposition,113 potentio-
static deposition114,115 and by the exchange reaction of
PAni with n-octadecyltrimethylammonium intercalated
manganese oxide.116 In general, improved capacitance of
the composites was reported. PAni is believed to be
partially involved in the Faradaic process, leading to
enhanced capacitance.113 On the other hand, it has been
proven that a low content of 5?6 wt-%MnO2 in the
MnO2/PAni composite can largely improve the cycling
stability of PAni, with only 3?5% loss after 5000 charge/
discharge cycles.114 However, a narrower operating
potential window115 and the severer capacitance loss113
during cycling were observed due to the addition of
PAni.
Composites of MnOx and other conducting polymers,
including poly(3-methylthiophene) (PMeT), poly(3,4-
ethylenedioxythiophene) (PEDOT) and polypyrrole
(PPy), were also synthesised. MnO2/PEDOT coaxial
nanowires were synthesised through electrocodeposition
in a porous alumina template.117 It was demonstrated
that the thickness of PEDOT shell and the length of
nanowire can be easily controlled by varying the applied
potential. The composite displayed a specific capaci-
tance of 185 F g21 at 25 mA cm22, because of the
porous nature of PEDOT shell that allowed fast ion
diffusion into the core MnO2 of the coaxial nanowires
and the high electrical conductivity of the PEDOT shell
that facilitates electron transport to the core MnO2.117
Also, the MnO2/PMeT composite was synthesised by
galvanostatic deposition of PMeT onto a Ti substrate,
and then MnO2.118 Scanning electron microscopy
images revealed that the introduction of PMeT led to
an irregular and porous morphology, thus larger active
area and more susceptible sites for redox reaction were
realised, which enhanced the capacitive performance.118
Ternary composite of CNT/PPy/hydrous MnO2 was
prepared by an in situ chemical method with a specific
capacitance of 281 F g21 measured at scan rate of
20 mV s21 in 1 mol dm23 dNa2SO4. A 10 000 cycle
reversibility test between 0?1 and 0?9 V at 100 mV s21
showed only 12% loss of its initial capacity. The
enhancement was attributed to the improved electrical
conductivity and a better dispersion of MnO2 in the
composite with the addition of PPy.119
However, the fundamental synergic effects are yet to
be clarified and not all the attempts in combining
conducting polymer and MnOx yielded positive results.
Recently, an attempt was made to deposit MnO2 onto a
three-dimensional matrix of poly(3,4-ethylenedioxythio-
phene)poly(styrene sulfonic acid)polyaniline
(PEDOTPSSPAni) through anodic deposition.120 An
enhanced the conductivity was expected as by incorpor-
ating PAni, the distance for electron shuttling along the
conjugated polymeric chain is decreased. However, a
Energy Materials 2008 VOL 3 NO 3 195
 Zhang and Chen Manganese oxide based materials for supercapacitors
a, b mesoporous carbon with template structure; MnO2/carbon composite from chemical precipitation;131 c fibrous man-
ganese oxide on highly porous nickel substrate132
8 Manganese oxides with mesoporous structures
low specific capacitance of 61?5 F g21 was recorded for
the composite in 3 mol dm23 KCl and only 68% of it
retained after 500 cycles between 0 and 1 V at
100 mV s21.120
Published by Maney Publishing (c) IOM Communications & W S Maney & Son Ltd
Nanostructured
With the development of nanotechnology, MnOx with
patterned mesoporous structures and nanostructures,
e.g. nanowires,121123 nanorod,124 nanoarray,125,126
nanoflower,127 nanoplates,60,128 microsphere,123 etc.,
have been successfully synthesised with various techni-
ques over the years. Interesting characteristics have been
found with these nanostructured materials. Some
researchers explored the possibility of promoting the
capacitive behaviour with these nanostructured MnOx
and gained positive results.
With mesoporous structure
Considering the performance limitations described in
the section on Important parameters influencing the
pseudocapacitive performance, a hybrid electrode
architecture that incorporates nanoscopic MnO2 at the
surface of a porous, high surface area and electronically
conducting structure (e.g. carbon nanofoams, templated
mesoporous carbon and nanotube/nanofiber assemblies)
may optimise both the electrochemical performance and
mass loading of an ultrathin MnO2 phase.
One of the common attempts in the pursuit of MnO2
with mesoporous structure is to chemically deposit
MnO2 onto structured advanced carbon material
(Fig. 8a and b). The mesoporous structures of carbon
materials can be original,87,129,130 or synthesised with
hard templates.131 It was reported that the mesoporous
structure of the carbons were not destroyed during
MnO2 chemical deposition.129 The carbon materials
acted as a highly conductive current collector; and the
well connected porosity served as a continuous pathway
for electrolyte transport.87 Although high specific
capacitance of 547 F g21 was reported for the
MnO2,129 the performance of the composite as a whole
is inadequate, due to the low loading of MnOx onto the
carbon materials (e.g. 10 wt-%).129,131 Also, the current
response is not as rapid as expected, as most of the
characterisations were carried out at scan rates
(5 mV s21. However, researchers are still confident
that further enhancement can be achieved by the
optimisation of the pore structure of the carbon
nanofoam and the MnO2 deposit thickness.87,130
Another approach is to synthesise MnO2 with ordered
mesoporous structures (Fig. 8c), by depositing or
dispersing MnO2 onto templates with desirable meso-
porous structures, followed by the dissolution of
the templates.127,132,133 Improved pseudocapacitive
196 Energy Materials 2008 VOL 3 NO 3
behaviour was observed even at a high scan rate of
100 mV s21,127,133 due to the contributions of the
surface of macropores and the interlayer space of the
multilayered structure.133
With high aspect ratio and arrayed structures
Recently, nanostructured materials with high aspect
ratio, e.g. nanofibers, nanotubes and nanowires, have
attracted great attention due to their unique mechanical
and electrical properties. They have introduced a new
aspect in the overall behaviour of bulk and surface
processes.134 Also, encouraging results have been
reported from the researches in electrode materials for
lithium ion battery: tubular structured electrode materi-
als, e.g. TiS2,135 V2O5136 and SnO2,137 exhibit improved
rate capabilities and extended cycle life compared with
the same material in the thin film form. Therefore,
similar efforts have been extended into the study of
MnOx.
Tubular shaped139 and more interestingly, highly
ordered nanowire arrays (Fig. 9a)125,126,140 of MnO2
have been successfully synthesised and explored for their
capacitive behaviour. The rod shaped MnO2, with the
length of 250350 nm and a diameter of 1015 nm,
synthesised through coprecipitation of KMnO4 and
MnCl2 under high viscosity controlled by polyethylene
glycol and polyacrylamide,139 was confirmed to be a-
and c-MnO2 by X-ray diffraction. Freestanding nano-
wires arrays have been prepared with anodic aluminium
oxide templates from electrodeposition125,126 and
the solgel route.140 Nevertheless, no exceptional elec-
trochemical performance was recorded with these
materials.
More recently, excellent specific capacitance of
199 F g21 (305 F cm23) and high cycling stability of
3% loss after 20 000 charge/discharge cycles were
declared with MnOx/CNT nanoflowers138 (Fig. 9c
and d). The MnOx/CNT nanoflowers were synthesised
by electrodeposition of MnOx onto the vertically grown
aligned CNT array. The exceptional performance of this
nanostructured composite is attributed to the following
factors: the aligned CNTs connecting MnOx and the Ta
foil are highly conducting, thus guaranteeing the
efficient charge transport and good electronic conduc-
tivity. In addition, a large surface area of 234 m2 g21
made the composite highly accessible. Moreover, the
hierarchically porous structure ensured high flowrate
due to convection, and the macropores functioned as ion
buffering reservoirs to minimise the diffusion distances.
It should be kept in mind that not all nanostructured
MnOx are advantageous in the capacitive performance,
thus the nanostructure itself is not the final pursuit. For
example, the hydrothermal route has been proven to be

Published by Maney Publishing (c) IOM Communications & W S Maney & Son Ltd
a MnO2 nanowire arrays grown on AAO/Ti/Si substrate;126 b MnO2/MWCNTs nanoball by microwave irradiation;128 c, d
SEM and TEM images of MnOx/CNTA nanoflowers138
9 Nanostructured manganese oxides
an effective and controllable method to produce MnOx
with various nanostructures.121,124 With this method,
MnO2 with various nanostructures, nanowhiskers,
nanoplates and nanorods, have been produced, simply
by increasing the hydrothermal dwell time.60 It was
found that crystallinity increased with respect to the
increase in the hydrothermal reaction time. However,
the MnO2 with amorphous structure showed the best
capacitive behaviour among all the products.60 On the
other hand, some subtle changes in the synthesis process
could result in different outcomes. It has been demon-
strated that by simply adding CNTs during the chemical
deposition of MnO2 under microwave irradiation, the
resultant ball shaped composite built-up of nano-
plates128 (Fig. 5b), a structure similar to the one
mentioned above,60 exhibited good electrochemical
capacitance of 298 F g21, due to the interlacement
structure of MnO2 nanoplates and CNTs.128
Cell performance
Although extensive studies have been conducted in the
synthesis and characterisations of MnOx for the
application as an electrode material for supercapacitors,
very few of them were extended to the characterisation
of cell performance, partly because the low loading of
MnOx may result in disappointing cell capacitance and
power characteristics.
Symmetric cell
Traditionally, electrochemical capacitors have a sym-
metric structure, especially for those made of carbon
materials with high surface areas. The total cell
capacitance is determined by the electrode with a smaller
value of the capacitance (equation (11)). Therefore, the
Zhang and Chen Manganese oxide based materials for supercapacitors
maximum cell capacitance is to be achieved when the
two electrodes have identical capacitance.
1 1 1
~ z (11)
Ccell Cpositive Cnegative
In addition, energy density and power density, which
can be derived from equations (12) and (13) respectively,
are the two widely used characterisations for super-
capacitors for their real world applications. It is worth
pointing out that energy and power densities are both
related with the cell voltage and can only be meaningful
for a cell or a stack of multiple cells. They should not be
used to describe individual electrode materials.
1
E~ Cm V 2 (12)
2
P~VImax (13)
where Cm is the mass specific capacitance and V is the
operating potential window.
Symmetrical two electrode cells with a-MnO2.nH2O/
CNT composite,72 MnO2141 and ternary composite of
CNT/PPy/MnO2119 as the electrode materials were
fabricated respectively. Interestingly, it was found out
that the two identical electrodes of the symmetric cell,
however, work in different potential range,72 namely,
after charging the cell to 0?6 V, the polarisation of the
negative electrode (E50?32 V) is larger than the
polarisation of the positive electrode (E50?28 V).72 In
a cell configuration like this, the limited operating
potential window is a major drawback,72,119,141,142 as a
small operating potential window affects the energy and
power performance directly (equations (12) and (13)).
Moreover, the electrochemical stability is a fundamental
Energy Materials 2008 VOL 3 NO 3 197
 Zhang and Chen Manganese oxide based materials for supercapacitors
a MnOx v. activated carbon electrode in 2 mol dm23 KNO3 electrolyte, scan rate 10 mV s21;144 b second and 1000th
CVs of asymmetrical cell of CNTs/SnO2 v. CNTs/MnO2 nanocomposites in 2 mol KCl at scan rate of 70 mV s21 (Ref. 93)
10 Performance of hybrid cells
issue. The negative electrode of the symmetric cell was
Published by Maney Publishing (c) IOM Communications & W S Maney & Son Ltd
reported to operate in the range of an irreversible
Mn(IV) to Mn(II) reaction, which results in the
dissolution of the electrode142 and consequently, poor
cycling stability.119,142
Hybrid cells
Owing to the disadvantages of the symmetric cells,
hybrid cells employing asymmetric electrodes with
different operating voltage windows were proposed.82
A prominent advantage of the hybrid cell system is the
enlarged operating potential window, which noticeably
enhances the energy and power performance (equa-
tions 12 and (13)). In aqueous systems, this is of
particular interest as it may allow the capacitor to be
operated at a potential window wider than the water
decomposition voltage of 1?2 V, if electrode materials
with high overpotentials for hydrogen or oxygen
evolutions are carefully selected.93 One particular issue
with hybrid supercapacitors is non-linear chargedis-
charge,143 nevertheless promising results from various
research groups indicated that this can be avoided by
appropriate cell fabrication.
With carbon materials
Carbon materials, with their well known advantages of
high overpotential for hydrogen evolution, good double
layer capacitive behaviour, excellent cycling stability and
electrical conductivity are undoubtedly a favourable
choice for the MnOx asymmetric cell.
Hybrid supercapacitors with MnOx as the cathode
and carbon materials such as activated car-
bon82,84,141,144,145 and multiwalled CNTs91 as the anode
have been fabricated. These hybrid systems exhibited
superior capacitive behaviour in comparison with the
symmetrical MnOx systems. Operating potential win-
dows at or larger than 2 V (Fig. 10a) were realised in
most cases.82,141,144,145 Although it was pointed out that
by narrowing the operating potential window to 1?5 V, a
better cycling stability can be achieved,145 since the
reduction of Mn4z to soluble Mn2z species, and
hydrogen and/or oxygen evolution occurred when the
hybrid cell was cycled over an operating potential
window of 2?2 V.145 However, a 24% decrease in the
initial energy density was still observed with this hybrid
cell after 23 000 cycles tested between 0 and 1?5 V in
0?65 mol dm23 K2SO4,145 which was believed to be
caused by the ions being trapped in the MnO2 electrode,
blocking the active sites, rather than the dissolution of
Mn(IV).145
198 Energy Materials 2008 VOL 3 NO 3
With other active materials
Metal oxides, including Fe3O4,146 LiMn2O4147 and
SnO2,93 were examined as the counter electrode materi-
als for MnOx to form the hybrid cells. The Fe3O4/MnO2
cell exhibited an operating potential window of 1?8 V in
the aqueous solution,146 although the cell performance
was later described to be inferior to the MnO2/carbon
cell.141 It provided a cheaper alternative to activated
carbon. A semibattery structure with MnO2/CNT and
LiMn2O4 as electrodes was characterised in 1 mol dm23
LiClO4 in polycarbonate, with specific energy of
56 Wh kg21 and a specific power of 300 W kg21. It is
worth mentioning that in a hybrid cell of SnO2/MnO2,
the MnO2/CNTs composite was explored as the anode
material, different from the common understanding that
MnO2 is a type of cathode material. An operating
potential window of 1?7 V (Fig. 10b)93 was achieved in
aqueous electrolytes, and an energy density of
20?3 Wh kg21 was obtained at the current density of
0?25 A g21 with only 8% loss of its capacitance after
1000 cycles.93
Conducting polymers, including PAni, PPy and
PEDOT, have been respectively fabricated into hybrid
supercapacitors with MnOx.142 Compared with the
MnOx/carbon hybrid cell, the MnOx/conducting poly-
mer cells exhibit higher capacitance, but narrower
operating potential windows in aqueous solutions: 1?2,
1?4 and 1?8 V for a-MnO2/PAni, a-MnO2/PPy and a-
MnO2/PEDOT respectively.148 These figures are still
considerably higher than the symmetric MnOx cells.
Conclusion
Recent research progresses in relation to manganese
oxides for supercapacitor applications have been criti-
cally reviewed. The pseudocapacitance of MnOx is
faradaic in nature and has been, for the first time,
qualitatively explained according to the band theory for
semiconductors, which should be generic for many other
transition metal oxides and conducting polymers.
Emphasis has been given to the synthesis and the
electrochemical behaviour, particularly charge storage,
of various forms of pure and composited MnOx.
Important parameters that can influence the electro-
chemical behaviour of MnOx based materials are
summarised. The engineering of MnOx with suitable
materials of complementary properties to form a
composite, or into specifically effective nanostructures
to assist charge transport, represents an important

direction of the development. Appropriate cell config-
uration has been proven to be the necessity for the
optimisation of the capacitive performance of MnOx
based supercapacitors. Based on these literature find-
ings, the authors believe that manganese oxides repre-
sent a promising and very competitive electrode material
for applications in supercapacitors.
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